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Treatment Performance Evaluation of Conventional Fenton Process

and Electro-Fenton Process Using Two Different Electro-Fenton


Reactors for Aniline Degradation

Eric D. Pagaling
BS Chemical Engineering

A Thesis presented to the Graduate Division


College of Engineering
University of the Philippines

In Partial Fulfillment of the Requirements


For the Degree of Master of Science in
Environmental Engineering

College of Engineering
University of the Philippines
Diliman, Quezon City

2006
ACKNOWLEDGEMENT

This thesis could not have been accomplished without Dr. Gene Peralta and Dr.
Ming-Chun Lu, who not only served as advisers but also challenged me throughout the
duration of my research and never accepting less than my best efforts. I also thank them
for giving me the opportunity not only on acquiring incalculable quantities of technical
knowledge but also on learning and appreciating other Asian cultures as well.

I also thank Dr. Ernie De la Cruz and Dr. Marilou Dalida for their persistence and
valuable contributions in refining this manuscript.

I am also thankful for the financial support given by the National Science Council
of Taiwan, Republic of China through Grant No. NSC94-2211-E-04-002 and the U.P.
Chemical Engineering Alumni Foundation Inc. (UP ChEAFI) through the efforts of Ms.
Louernie F. De Sales-Papa.

I am also grateful for the support given to me throughout my research and


academic program by Laarni Panopio, Lorenzo Lim, Nolan Tolosa, Ate Babes Ali, Jobert
Papa, Prof. Jun Ballesteros and Gemma Seminiano of the Environmental Engineering
Graduate Program of UP Diliman. I also thank Kuan-Shien Ho, Yi-Chun Tsai, Wan-Ping
Ting, Wan-Shu Hsu, Shin-Yi Tu, Chun-Yi Li and Su-Yi Wang of Chia Nan University of
Pharmacy and Science; Massakul Kitmongkonsak and Somboon Chintitanun of
Chulalongkorn University; Nonglak Boonrattanakij, Aroon Khongnou, Witchuda Aui-
aree, Praphat Siriruang, Wichidtra Sudjarid, Rosenee Sama-ae of King Mongkut’s
University of Thonburi Thailand; Nguyen Duy Hung, Pham Minh Tu and Tran Phuong
Ha of Hanoi University of Technology.

Lastly I thank my family for the ceaseless support and encouragement in this
research and in all of my endeavors. This thesis is sincerely dedicated to all of you.
ABSTRACT

Aniline degradation was investigated using the conventional Fenton (CF) process
and electro-Fenton (EF) process employing the plate type electrode and rod type
electrode EF reactors with IrO2/RuO2 coated titanium metal anodes and stainless steel
cathodes. The treatment performance evaluation of the two EF reactors was conducted by
determining the effects H2O2, Fe2+, electric current and initial aniline concentration on the
aniline and COD removal efficiencies, initial aniline degradation rates, kinetic models,
H2O2 efficiency and power consumption for aniline and COD removal. Aside from this
the change in the BOD, toxicity and oxalic acid production of a high initial aniline
concentration having 10,000ppm COD was also studied using the two EF reactors.

The EF process was superior to the CF process due to its higher treatment
efficiency at low Fe2+ concentrations, low inorganic sludge production and low residual
H2O2 after treatment. Both of the EF reactors have the same aniline and COD removal
efficiencies at high H2O2 concentrations however at H2O2 concentrations lower than
58mM, the plate type electrode EF reactor was superior to the rod type electrode EF
reactor. An increase in H2O2 and Fe2+ concentrations lowered power consumptions for
aniline and COD removal for both of the EF reactors. However increase in H2O2 greater
than 58mM and Fe2+ greater than 1.61 mM had no further effect on power consumption
due to decreased aniline and COD removal efficiencies. The rod type electrode EF
reactor consumes twice as much power for aniline and COD removal than the plate type
electrode EF reactor and that COD removal requires twice as much power than aniline
removal. Increase in applied electric current increases the difference in the power
consumption between the rod type electrode and plate type electrode EF reactors from 1.7
to 3.3 times. Treatment of high concentration aniline solution resulted into an increased
BOD and lowered toxicity values of 0.18 and 0.25 for the plate type electrode and rod
type electrode EF reactors respectively. The plate type electrode EF reactor was found to
be more versatile than the rod type electrode EF reactor since it can be operated at
different Fe2+ concentrations and at higher electric current applications.
TABLE OF CONTENTS

I. Introduction…………………………………………………………………... 1
1.1 Objective of the study………………………………………………… 2
1.2 Scope and limitations…………………………………………………. 3

II. Review of Related Literature………………………………………………. 4


2.1 Advanced oxidation processes………………………………………... 4
2.2 Conventional Fenton process…………………………………………. 6
2.3 Photo-Fenton, Fenton-like, electro-Fenton and photo electro-Fenton
processes................................................................................................ 9
2.4 Uses and properties of aniline………………………………………… 11
2.5 Aniline degradation using different Fenton processes………………... 12

III. Methodology………………………………………………………………... 14
3.1 Electro-Fenton reactors……………………………………………….. 14
3.2 Materials and reagents.………………………………………………... 14
3.3 Experimental procedures……………………………………………… 16
3.4 Sampling and laboratory analysis…………………………………….. 17
3.5 Statistical analyses methods…………………………………………... 18
3.6 Kinetic modeling method……………………………………………... 18

IV. Results and Discussion…………………………………………………… 19


4.1 Aniline degradation using conventional Fenton and electro-Fenton
Processes………………………………………………………………. 19
2+
4.2 Fe regeneration efficiency of the plate type electrode and rod
type electrode EF reactors……………………………………………... 23
4.3 Effect of H2O2, Fe2+, electric current and initial aniline
concentration on the aniline degradation efficiency using the plate
type electrode and rod type electrode EF reactors……………………. 24

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4.4 Effect of H2O2, Fe2+, electric current and initial aniline
concentration on the initial aniline degradation rate using the plate
type electrode and rod type electrode EF reactors……………………. 32
2+
4.5 Effect of H2O2, Fe , electric current, initial aniline degradation rate
on the second order aniline degradation rate constant using the plate
type electrode and rod type electrode EF reactors……………………. 36
4.6 Effect of H2O2, Fe2+, electric current, initial aniline concentration on
the COD removal efficiency using the plate type electrode and rod
type electrode EF reactors…………………………………………….. 40
2+
4.7 Effect of H2O2, Fe , electric current, initial aniline concentration on
the H2O2 efficiency for aniline and COD removal using the plate
type electrode and rod type electrode EF reactors……………………. 44
4.8 Effect of H2O2, Fe2+, electric current and initial aniline
concentration on the power consumption for aniline and COD
removal using the plate type electrode and rod type electrode EF
reactors………………………………………………………………... 49
4.9 Degradation of high initial aniline concentration……………………… 54

V. Conclusions………………………………………………………………….. 57

VI. Recommendations for Future Work……………………………………… 60

References………………………………………………………………………. 61

Appendices…………………………………………………………………….... 66
Appendix A. Aniline degradation rate constant calculations……………... 67
Appendix B. Raw data……………………………………………………. 75
Appendix C. Sample statistical analyses calculations……………………. 83
Appendix D. Photographs of the electro-Fenton reactors………………… 86

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LIST OF TABLES

Table Title Page

2-1 List of reactive compounds with their respective oxidation power 7

4-1 Effect of H2O2 on the aniline degradation efficiency using the plate 27
type electrode and rod type electrode EF reactors

4-2 Effect of Fe2+ on the aniline degradation efficiency using the plate 29
type electrode and rod type electrode EF reactors

4-3 Effect of electric current on the aniline degradation efficiency 30


using the plate type electrode and rod type electrode EF reactors

4-4 Effect of initial aniline concentration on the aniline degradation 31


efficiency using the plate type electrode and rod type electrode EF
reactors

4-5 Effect of H2O2 on initial aniline degradation rate using the plate 32
type electrode and rod type electrode EF reactors

4-6 Effect of Fe2+ on the initial aniline degradation rate using the plate 33
type electrode and rod type electrode EF reactors

4-7 Effect of electric current on the initial aniline degradation rate 34


using the plate type electrode and rod type electrode EF reactors

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4-8 Effect of initial aniline concentration on initial aniline degradation 35
rate and aniline removal efficiency using plate type electrode and
rod type electrode EF reactors

4-9 Effect of H2O2 on the COD removal efficiency using the plate type 40
electrode and rod type electrode EF reactors

4-10 Effect of Fe2+ on the COD removal efficiency using plate type 41
electrode and rod type electrode EF reactors

4-11 Effect of electric current on the COD removal efficiency using 42


plate type electrode and rod type electrode EF reactors

4-12 Effect of initial aniline concentration on the COD removal 43


efficiency using the plate type electrode and rod type electrode EF
reactors

4-13 Effect of H2O2 on the H2O2 efficiencies for aniline and COD 45
removal using the plate type electrode and rod type electrode EF
reactors

4-14 Effect of Fe2+ on the H2O2 efficiency for aniline and COD removal 46
using the plate type electrode and rod type electrode EF reactors

4-15 Effect of electric current on the H2O2 efficiency for aniline and 47
COD removal using the plate type electrode and rod type electrode
EF reactors

4-16 Effect of initial aniline concentration on the H2O2 efficiency for 48


aniline and COD removal using the plate type electrode and rod
type electrode EF reactors

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LIST OF FIGURES

Figure Title Page

2-1 Aniline degradation pathway using the Fenton process 13

3-1 Schematic diagrams of the plate type electrode and rod type 15
electrode electro-Fenton reactors

3-2 Experimental procedure summary flowchart 17

4-1 Effect of conventional Fenton and electro-Fenton processes on 19


aniline degradation and COD removal using [Fe2+] = 0.27mM and
[H2O2] = 58mM

4-2 Effect of conventional Fenton and electro-Fenton processes for 20


aniline degradation and COD removal using [Fe2+] = 1.07mM and
[H2O2] = 58mM

4-3 Residual H2O2 from aniline degradation using conventional 22


Fenton and electro-Fenton processes

4-4 Fe2+ regeneration efficiency of the plate type electrode and rod 23
type electrode EF reactors

4-5 Effect of H2O2 on aniline degradation using plate type electrode 24


and rod type electrode EF reactors

4-6 Effect of Fe2+ on aniline degradation using the plate type electrode 25
and rod type electrode EF reactors

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4-7 Effect of electric current on aniline degradation using the plate 25
type electrode and rod type electrode EF reactors

4-8 Effect of initial aniline concentration on aniline degradation using 26


the plate type electrode and rod type electrode EF reactors

4-9 Effect of H2O2 on the second order aniline degradation rate 36


constant using the plate type electrode and rod type electrode EF
reactors

4-10 Effect of Fe2+ on the second order aniline degradation rate 37


constant using the plate type electrode and rod type electrode EF
reactors

4-11 Effect of electric current on the second order aniline degradation 38


rate constant using the plate type electrode and rod type electrode
EF reactors

4-12 Effect of initial aniline concentration on the second order aniline 39


degradation rate constant using the plate type electrode and rod
type electrode EF reactors

4-13 Effect of H2O2 on the power consumption for aniline and COD 50
removal using the plate type electrode and rod type electrode EF
reactors

4-14 Effect of Fe2+ on the power consumption for aniline and COD 51
removal using the plate type electrode and rod type electrode EF
reactors

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4-15 Effect of electric current on the power consumption for aniline and 52
COD removal using the plate type electrode and rod type electrode
EF reactors

4-16 Effect of initial aniline concentration on the power consumption 53


for aniline and COD removal using the plate type electrode and
rod type electrode EF reactors

4-17 Aniline and COD remaining ratios from degradation of 54


10,000ppm COD of aniline using the plate type electrode and rod
type electrode EF reactors

4-18 BOD and toxicity tests on treated high concentration aniline 55


solution using the plate type electrode and rod type electrode EF
reactors

4-19 Oxalic acid content of the treated high concentration aniline 55


solution using the plate type electrode and rod type electrode EF
reactors

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I. INTRODUCTION

Treatment of wastewater contaminated with recalcitrant and toxic compounds


using chemical oxidation technologies has been an interest in recent studies because of
the increasing generation of such wastes and the inability of existing technologies for
treatment and remediation.

Application of Advanced Oxidation Processes (AOPs) for treatment has been


studied extensively and has been found to be highly efficient. AOPs generate radical
intermediate compounds that are highly oxidative species. These radical intermediate
compounds oxidize toxic pollutants into harmless species and are generated by systems
that utilize technologies like the Fenton process, photocatalysis and cavitation.

Among the current AOP technologies, the Fenton process is the most cost
effective and has already been applied in full scale wastewater treatment operations. The
Fenton process produces highly oxidative hydroxyl radical species from the reaction of
hydrogen peroxide (H2O2) and Ferrous ions (Fe2+). Since its inception, the Fenton process
has been modified to increase its efficacy and solve operational problems. Fenton
technologies include the conventional Fenton (CF) process, electro-Fenton (EF) process,
photo-Fenton process, Fenton-like process and the photo electro-Fenton process.

One of the potential Fenton technologies is the EF process. The EF process


utilizes H2O2 and Fe2+ to produce hydroxyl radicals inside an electrochemical system.
The EF process was designed to solve excessive inorganic sludge production of the CF
process by electro regeneration of Fe2+ from Ferric ions (Fe3+).

The electro-Fenton process employing a rod type electrode was first used for full
scale applications due to its advantage over the conventional Fenton process. However
the rod type electrode EF reactor also had several disadvantages because of limitations in
its design. These problems include high power consumption and difficult maintenance

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procedures during electrode fouling problems. Because of this, the plate type electrode
EF reactor was proposed as an alternative. However the difference in the treatment
performance between the two EF reactors was not known.

In this regard the treatment performance of the CF process and EF process


employing the plate type electrode and rod type electrode EF reactors, having the same
materials of construction, was studied in order to determine their respective optimum
operating conditions using aniline as the target organic pollutant.

Aniline was chosen as the target organic pollutant since aniline degradation was
previously studied using different Fenton processes including EF reactors with different
designs and experimental conditions. In addition to this, aniline is also a recalcitrant
organic compound and has been found to be toxic to human health and aquatic life.

1.1 Objective of the Study

The main objective of the study was to evaluate the treatment performance of the
conventional Fenton process and the electro-Fenton process employing the plate type
electrode and rod type electrode electro-Fenton reactors for aniline degradation. The
specific objectives of the study were to determine and compare the:
1. Treatment performance between the CF and EF process
2. Fe2+ regeneration efficiency of the plate type electrode and rod type electrode EF
reactors
3. Effects of H2O2, Fe2+, electric current and initial aniline concentration using the
two EF reactors on the following parameters:
3.1 Aniline removal efficiency
3.2 Initial aniline degradation rate
3.3 Aniline degradation rate constant
3.4 COD removal efficiency

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3.5 H2O2 efficiency for aniline and COD removal
3.6 Power consumption for aniline and COD removal
4. Change in the BOD and toxicity of a 10,000ppm COD aniline solution using the
two EF reactors.

1.2 Scope and Limitations

The study focused on the use of the conventional Fenton process and electro-
Fenton process using the plate type electrode and rod type electrode EF reactors for the
degradation of aniline.

Treatment performance evaluation was limited to the results of laboratory scale


experiments using synthetic wastewater containing aniline. Actual application of the
conventional Fenton and electro-Fenton processes on real wastewaters was not conducted
in the study.

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II. REVIEW OF RELATED LITERATURE

2.1 Advanced Oxidation Processes

Advanced oxidation processes (AOPs) generate radical intermediate compounds


that are highly oxidative species. These radical intermediate compounds degrade toxic
and recalcitrant organic pollutants to harmless species and are generated through
specially designed equipments or reaction of certain chemicals. Examples of AOP
technologies include cavitation, photocatalytic oxidation and the Fenton’s process.

In cavitation, radical intermediate compounds are formed from the very fast
production and sudden collapse of microbubbles or cavities. Cavitation is being done
through the use of ultrasonic irradiation equipments or constrictions in hydraulic devices
(Gogate 2004). Radical intermediate compounds are formed from acoustic cavitation
through the use of high frequency sound waves or ultrasounds. Acoustic cavitation has
been applied on the degradation of different compounds like propionic acid (Yoo 1997)
and 3-chloroaniline (David 1998). Hydrodynamic cavitation produces radical
intermediate compounds by passing the liquid into a constriction. Hydrodynamic
cavitation has been applied for the treatment of compounds like ethyl benzene, xylenes,
cyanide and phenol (Gogate 2004).

Radical intermediate compounds are formed in photocatalytic oxidation by using


ultraviolet radiation or near UV light on wastewaters containing photochemically
degradable compounds like H2O2 or ozone. Photochemical oxidation has also been
conducted with the use of a semiconductor catalyst like titanium dioxide to enhance the
generation rates of radical intermediate compounds (Gogate 2004). Photochemical
oxidation has been applied for treatment of compounds like chlorophenols (Trapido
1997) and perchloroethylene (Gupta 1995).

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The Fenton process produces radical intermediate compounds by the reaction of
H2O2 and Fe2+. The Fenton process has been applied in wastewater treatment processes
and is known to be very effective in the removal of many hazardous organic pollutants
(Neyens 2003). Radical intermediate compounds produced from the Fenton process is
composed mostly of hydroxyl radicals. Hydroxyl radicals exhibit faster rates of oxidation
reactions as compared to those using conventional oxidants like hydrogen peroxide or
permanganate (Gogate 2002).

Application of the Fenton process on oxidation of different refractory pollutants


in soil media and aqueous solutions has been done extensively since its conception. For
aqueous solutions, refractory pollutants that were investigated includes phenols and alkyl
hydrocarbons (Gao 2004), polyphenols and aromatic compounds (Peres 2004), pesticides
(Rivas 2004; Chan 2003), ethylenediaminetetraacetic acid (EDTA) (Ghiselli 2004),
surfactants (Gaca 2005), explosives (Liou 2003), phenol (Kavitha 2004), dyes (Meric
2003; Dutta 2003; Muruganandham 2004), MTBE (Xu 2004), microcystins (Bandala
2004), nitroaromatic compounds (Trapido 2003), p-nitrophenol (Khan 2005) and
dichlorvos (Lu 1999).

The Fenton process was also used in the treatment of actual wastewater with
mixtures of different refractory pollutants like pharmaceutical wastewater (Martinez
2003), sanitary landfill leachate (Rivas 2003) and (Lopez 2004), Oilfield wastewater
(Gao 2004), Table olive processing wastewater (Kotsou 2004) and cork cooking
wastewater (Guedes 2003).

The Fenton process has also been applied for contaminated soil remediation.
Examples of refractory pollutants investigated in studies on soil media include n-alcohols
(Quan 2003), trichloroethylene (TCE) and tetrachloroethylene (PCE) (Go 2003;
Baciocchi 2004) and petroleum (Millioli 2003).

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Applications of the Fenton process other than toxic and recalcitrant compound
degradation in aqueous solutions and soil matrices includes treatment of a bacteria
containing solution (Barbusinski 2005), removal of harmful disinfection by-products by
treatment of natural organic matter prior to chlorination (Murray 2004), sludge
conditioning (Buyukkamaci 2004), regeneration of activated carbon saturated with
organochloro compounds (Toledo 2003), polycyclic aromatic hydrocarbon degradation in
municipal sewage sludge (Flotro 2003) and activated sludge dewatering (Lu 2003)

The Fenton process has been modified in recent years in order to increase its
efficacy and solve operational problems. Fenton technologies now include the electro-
Fenton process, photo Fenton process, photo electro-Fenton process and Fenton-like
process. In order to differentiate the original Fenton process from the new and emerging
Fenton technologies, it is referred in this study as the conventional Fenton process.

2.2 Conventional Fenton Process

The conventional Fenton process was first discovered and used by H. J. H. Fenton
in 1894 when he observed that the rate of oxidation of tartaric acid increased dramatically
when dilute hydrogen peroxide was added with the solution containing dissolved Fe2+
ions. Fenton’s chemistry is a reaction between hydrogen peroxide and Fe2+ forming
hydroxyl radicals, which is the main oxidizing agent. However the hydroxyl radical
mechanism of the Fenton’s reaction was only identified 40 years after its discovery
(Watts 2005).

Hydroxyl radicals (OH·) are short-lived reactive oxygen species with a high
oxidation potential that can rapidly destroy many biorefractory contaminants (Watts
2005). It is one of the most reactive chemical species, second only to elemental fluorine
in its relative oxidation power as listed in Table 2.1 (Barbusinski 2005).

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Table 2-1: List of reactive compounds with their respective oxidation power.
Reactive Species Relative Oxidation Power
Flourine 2.23
Hydroxyl radical 2.06
Atomic oxygen 1.78
Hydrogen peroxide 1.31
Perhydroxyl radical 1.25
Permanganate 1.24
Chlorine dioxide 1.15
Hypochlorous acid 1.10
Chlorine 1.00
Bromine 0.80
Iodine 0.54

The hydroxyl radical is considered to be an electrophile due to a deficit of one


electron in its valence orbit. The most common reactions of hydroxyl radicals are
electrophilic substitution in aromatic compounds and addition to alkenes. Other chemical
reactions involving hydroxyl radicals include hydrogen abstraction forming an organic
free radical and water (Watts 2005).

The conventional Fenton process generates hydroxyl radicals through the reaction
of hydrogen peroxide with ferrous ions according to reaction (2.1) and with organic
radical compounds through reaction (2.2) (Watts 2005; Quan 2003).

Fe2+ + H2O2 Æ Fe3+ + OH- + OH· (2.1)


R· + H2O2 Æ ROH + OH· (2.2)

The organic radical compounds (R·) from reaction (2.2) are formed from the
reaction of organic compounds with excess hydroxyl radicals as shown in reaction (2.3)
(Meric 2003; Gao 2004).

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RH + OH· Æ R· + H2O (2.3)

The conventional Fenton process also yields other reactive oxygen species
through propagation reactions. These reactive oxygen species includes perhydroxyl
radical (HO2·) which is a relatively weak oxidant, superoxide radical anion (O2·-) which is
a weak reductant and is a nucleophile, and hydroperoxide anion (HO2-) which is a strong
nucleophile (Watts 2005). These non-hydroxyl radicals are formed according to the
reactions (2.4), to (2.8) (Watts 2005; Quan 2003; Trapido 2003; Guedes 2003; Gao 2004;
Meric 2003).

OH· + H2O2 Æ HO2· + H2O (2.4)


HO2· ÅÆ O2·- + H+ (2.5)
HO2· + Fe2+ Æ HO2- + Fe3+ (2.6)
HO2· + O2·- Æ HO2- + O2 (2.7)
2+ 2+
Fe-OOH Æ HO2· + Fe (2.8)

However scavenging reactions of hydroxyl radicals by H2O2 and Fe2+ and non
hydroxyl radicals by Fe3+ are also present in the conventional Fenton process like
reaction (2.4), (2.9) and (2.10) (Trapido 2003; Martinez 2003; Guedes 2003; Dutta 2003).

Fe2+ + OH· Æ Fe3+ + OH- (2.9)


Fe3+ + HO2· Æ Fe2+ + H+ + O2 (2.10)

Fe3+ produced from the Fenton process can react with excess H2O2, perhydroxyl
radicals, and organic radical compounds in the so-called Fenton-like reaction, which
leads to regeneration of Fe2+ according to reactions (2.11) to (2.14) (Trapido 2003;
Guedes 2003; Gao 2004; Meric 2003; Martinez 2003; Dutta 2003).

Fe3+ + H2O2 ÅÆ H+ + Fe-OOH2+ (2.11)


Fe-OOH2+ Æ HO2· + Fe2+ (2.12)
R· + Fe3+ Æ R+ + Fe2+ (2.13)

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Fe3+ + HO2· Æ Fe2+ + H+ + O2 (2.14)

Reactions (2.11) to (2.14) have been simplified by other studies into reaction
(2.15) (Martinez 2003; Dutta 2003; Peres 2004).

Fe3+ + H2O2 Æ Fe2+ + HO2· + H+ (2.15)

Inhibitions to the Fenton process have also been investigated in recent studies.
Anions like H2PO4, Cl-, NO3 and ClO4- was found to inhibit the Fenton reaction therefore
reducing its efficiency. Among the anions, H2PO4 was found to inhibit the reaction the
most since the phosphate ions will produce a complex reaction with ferrous and ferric
ions (Lu 1997). The inhibition of low concentration chloride ions was found to be
controlled by extending the reaction time. However inhibition is significant if the ratio of
chloride to ferrous ions is greater than 200. Likewise, inhibition by chloride ions was
controlled by increasing the initial pH near to 5 and increasing the amount of ferrous ions
(Lu 2005; Sajiki 2004). Presence of chloride ions in the Fenton process also produces
chloroorganic compounds as byproducts (Gaca 2005).

The effect of temperature on the rate of reaction of the Fenton process was also
studied and was found to increase as the solution temperature was increased. However
the effect of temperature was only obvious at temperatures lower than 20 0C. In addition
to this application of temperatures greater than 40 0C, the treatment efficiency declines
due to decomposition of H2O2 into oxygen and water. Application of the Fenton process
has been normally conducted at temperatures of 20 to 40 0C (Watts 2005).

The optimal pH range for the application of the Fenton process was also
determined to be at pH 3 and pH 6. Application of the Fenton process at high pH values
will result into inhibition of the Fenton reaction since the Fe2+ ions will form colloidal
Fe3+ ions. Likewise application of the Fenton process at very low pH values would result
into the decomposition of H2O2 into oxygen and water by iron without forming hydroxyl
radicals (Neyens 2003).

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2.3 Photo-Fenton, Fenton-like, electro-Fenton and Photo electro-Fenton processes

The conventional Fenton process has been modified such that the treatment
efficiency was increased with reduced inorganic slugged production, and prevention of
inhibition reactions of some ions. Among the emerging Fenton technology are the photo
Fenton, Fenton-like, electro-Fenton and Photo electro-Fenton processes.

The photo Fenton process utilizes UV to enhance the treatment efficiency by


regenerating ferrous ions produced from reaction (2.1). The efficiency was enhanced
when additional hydroxyl radicals are produced when the regenerated Fe2+ reacts with
excess H2O2. Studies have been conducted using photo Fenton on aqueous solutions
containing bisphenol A (BPA) (Katsumata 2004), explosives like 2,4,6- trinitrophenol
(PA), ammonium picronitrate (AP), 2,4-dinitrotoluene (DNT), methyl-2,4,6-
trinitrophenylnitramine (Tetryl) and 2,4,6-Trinitrotoluene (TNT), hexahydro-1,3,5-
trinitro-1,3,5-triazine (RDX) and octahydro-1,3,5,7- tetranitro-1,3,5,7-tetrazocine (HMX)
(Liou 2003), microcystin-LR toxin (Bandala 2004), natural organic matter (Murray
2004), chlorotriazine reactive azo dye specifically Reactive Orange 4 (RO4)
(Muruganandham 2004), phenol (Will 2004), dimethyl phthalate (DMP) (Zhao 2004) and
ethylenediaminetetraacetic acid (EDTA) (Ghiselli 2004).

Fenton-like process uses other transition metal catalyst other than Fe2+. This
modification reduces or completely eliminates the production of inorganic sludge. Some
studies investigated the use of Fe-containing zeolites (Kuznetsova, 2004), soluble
manganese (II) and amorphous and crystalline manganese (IV) oxides (Watts 2005),
soluble iron (III) and pyrolusite Sb-MnO2, (Watts 2005), heterogeneous catalyst (swarf)
(Barbusinski 2005) , Fe3+, Cu2+ and mixtures of Fe2+/Cu2+ and Fe3+/Cu2+ (Ghiselli 2004),
suspended iron powder (Liao 2003), laponite clay-based Fe nanocomposite (Fe-Lap-RD)
(Feng 2003), zero-valent iron (Bergendahl 2004) and strongly acidic ion exchange resin
(SAIER) (Feng 2004).

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The electro-Fenton process involves the use of the Fenton reagents in an
electrochemical system. This modification reduces sludge production by electro
regenerating Fe2+ ions from Fe3+ at the cathodes and Fenton reagent utilization by directly
producing H2O2 or Fe2+ or both through the electrochemical system.

The electro-Fenton technology has been modified in some studies to reduce the
use of Fenton reagents. Different electro-Fenton configurations included the production
of H2O2 or both hydrogen peroxide and ferrous ions using an electrochemical system (Lu
2004). Examples of cathodes that are used for the production of hydrogen peroxide
include O2 diffusion PTFE (Brillas 2002), graphite, reticulated vitreous carbon, mercury
pool and carbon felt (Brillas 2003). Anodes used for these systems are Ti/Pt mesh (Brillas
2002), Pt, boron doped diamond (Brillas 2004) and sacrificial iron (Lu 2004).

Another electro-Fenton technology only involves the electro regeneration of Fe2+


from Fe3+ according to reaction (2.16). With this technology, addition of Fe2+ and H2O2
into the solution is required. Different anodes used in this technology include Ti/Pt mesh
anode or DSA plate (Brillas 2002), Ti/Pt special net anodes (Anotai 2006) and IrO2/RuO2
coated Ti rod anode (Lu 2003).

Fe3+ Æ Fe2+ + e- (2.16)

Pollutants treated by this technology includes aniline (Brillas 2002; Lu 2003;


Anotai 2006), chlorophenoxy herbicides (Brillas 2004), 3,6-dichloro-2-methoxybenzoic
acid herbicide (Brillas 2003). The electro-Fenton process has also been used for the
treatment of non-biodegradable wastewater (Chang 2004).

The electro-Fenton has been further modified through the added use of UV to
further enhance its efficiency by destroying Fe3+ complexes with degradation by products
such as oxalic acids. This new technology was called the photo electro-Fenton and was
applied for the degradation of aqueous solutions of aniline, nitrobenzene, and 4-
chlorophenol (Casado 2005).

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2.4 Uses and Chemical Properties of Aniline

Aniline or aminobenzene is an oily, flammable liquid, with a clear to slightly


yellow color and a distinctive odor. Aniline has one amino group attached to a benzene
ring as the structure. This compound is slightly soluble in water and does not evaporate at
room temperature (ATSDR-TOXFAQS). This compound is mainly used as a raw
material for the production of other chemicals like isocyanates, polyurethane foams,
pesticides, dyes, rubber, drugs, photographic chemicals, varnishes and explosives. In
addition to this, the United States has considered aniline to be a High Production Volume
(HPV) compound because of an annual production of more than 1 billion pounds with an
increase in demand of 3% to 4% per year in the United States alone (EPA-HPV Chemical
List). However aniline is a recognized carcinogen, gastrointestinal toxicant, kidney
toxicant, neurotoxicant, respiratory toxicant, sense organ toxicant and is found to be
highly toxic to aquatic life (EPA-OPPT Chemical Fact Sheet 1994).

2.5 Aniline degradation using different Fenton processes

Aniline degradation studies using the Fenton process includes the conventional
Fenton and the electro-Fenton processes. Aniline degradation was investigated using the
conventional Fenton and electro-Fenton processes through a 4-step and 1-step addition of
H2O2 for a total reaction time of two hours. The study was conducted using an initial
aniline concentration of 10mM, 7,700ppm of H2O2 and 327ppm of Fe2+ for the
conventional Fenton process. The electro-Fenton process was conducted using the same
experimental condition but with the addition of 2A of electric current. The electro-Fenton
reactor used in the study had a titanium rod coated with RuO2/IrO2 as the anode and a
stainless steel as the cathode. It was determined in the study that the electro-Fenton
process was superior to the conventional Fenton process due to a COD removal of 90%
compared to an increased COD value for the conventional Fenton process after treatment.
It was also determined in the study that the 4-step addition of H2O2 remove slightly the
COD by 10% (Lu 2003).

12
Another study was conducted on aniline degradation using the conventional
Fenton process and the electro-Fenton process. The electro-Fenton reactor used in the
study had an anode and cathode of Ti/Pt special net and stainless steel nets respectively.
The H2O2 was added into the reactor in six equal parts every twenty minutes to ensure the
presence of H2O2. It was also determined from the study that the electro-Fenton process
was superior to the conventional Fenton process due to a difference of 1.2 to 3.1 times for
aniline removal efficiencies (Anotai 2006). An aniline degradation pathway was
proposed from another study and is shown in Figure 2-1 (Brillas 1998).

Nitrobenzene

Aniline Æ Phenol Æ Hydroquinone Æ Benzenetriol Æ Maleic acid Æ Oxalic acid ÆCO2

Benzoquinonimine Æ Benzoquinone

Figure 2-1: Aniline degradation pathway using the Fenton process.

Aniline degradation was also investigated using an electro-Fenton reactor with a


Ti/Pt mesh anode or DSA plate and a H2O2 producing cathode. The experimental
condition used in the study includes a 1,000ppm initial aniline concentration at an initial
pH of 3. It was determined in the study that a 61% TOC degradation was obtained at a
total reaction time of two hours using 20 A of electric current (Brillas 2002).

Another study on aniline degradation was also conducted using a plate type
electrode electro-Fenton reactor with an anode made of a Ti coated with RuO2/IrO2 and a
stainless steel cathode. It was determined from the study that the optimum initial pH was
at 3.2 using an initial aniline concentration of 10mM, 58mM of H2O2 and 1mM of Fe2+. It
was also determined from the study that H2PO4 inhibits the Fenton process more than
chlorides and that recycling of electro regenerated Fe2+ rich solution had no detrimental
effect on the treatment performance of the electro-Fenton reactor (Tsai 2006).

13
III. METHODOLOGY

3.1 Electro-Fenton Reactors

Aniline degradation experiments were carried out in two electro-Fenton (EF)


reactors with different electrode configurations, which were the plate type electrode and
rod type electrode. Both of the anodes and cathodes of the EF reactors were titanium
metals coated with IrO2/RuO2 and stainless steels, respectively. The plate type electrode
EF reactor had a plexiglas rectangular vessel with a 5L volume capacity (15 (W) x 21 (L)
x 20 (H) cm3). On the other hand the rod type electrode EF reactor had a stainless steel
cylindrical vessel that also serves as the cathode with a 1L volume capacity. Both of the
EF reactors were operated at a constant electric current of 0.8A/L and were provided with
mixers for appropriate agitation and connected to a Topward 33010D DC power supply.
The schematic diagrams of the plate type electrode and rod type electrode EF reactors are
shown in Figures 3-1 (a) and (b), respectively.

3.2 Materials and Reagents

The synthetic wastewater was prepared by using reagent grade aniline (≥ 99.5%)
from MERCK that was diluted with deionized water, from a Millipore system with a
resistivity of 18.2 MΩcm-1, to the desired aniline concentration. The prepared solutions
were adjusted to pH 3.2 using 25% H2SO4 that was prepared using reagent grade H2SO4
(acidimetric assay of 95-97%) from MERCK. pH was measured using a SUNTEX TS-1
portable pH/MV meter.

Reagent grade 35% H2O2 (manganometric assay of 35-36.5%) was supplied from
MERCK and the Fe2+ was obtained from reagent grade FeSO4·7H2O (manganometric
assay of 99.5-102%) that was also obtained from MERCK. For the Fe3+ reduction
experiments, reagent grade Fe2(SO4)3·nH2O from KANTO CHEMICAL CO., INC. was

14
diluted with deionized water to the desired concentration of 500ppm Fe3+ at an initial pH
of 2.

(a)

(b)

Figures 3-1: Schematic diagrams of the (a) plate type electrode and
(b) rod type electrode EF reactors

15
3.3 Experimental Procedures

The treatment performance evaluation using the conventional Fenton and electro-
Fenton processes were conducted using 10mM of aniline and 58mM of H2O2. Fe2+
concentration applied was at 0.27mM and 1.07mM. For both of the experimental
conditions, the electro-Fenton process was conducted using a constant electric current of
0.8A/L.

The effect of H2O2 was determined by varying the H2O2 concentration added into
the EF reactors from 14.5mM, 29mM, 58mM, 87mM and 130mM. All experimental
conditions used a constant Fe2+ concentration of 1.07mM, 10mM of aniline and an
applied electric current of 0.8A/L.

The effect of Fe2+ on aniline degradation was determined by varying the


concentration of the Fe2+ from 0.27mM, 0.54mM, 1.07mM, 1.61mM and 2.41mM using
a constant H2O2 concentration of 58mM, 10mM of aniline and 0.8A/L of applied electric
current. However the rod type electrode EF reactor was only operated at Fe2+
concentration greater then 1.07mM since the required 0.80A/L of electric current could
not be achieved due to decreased solution conductivity.

The effect of electric current on aniline degradation was determined by varying


the applied electric current from 0.2A/L, 0.4A/L, 0.8A/L, 1.2A/L and 1.8A/L using
10mM of aniline, 58mM of H2O2 and 1.07mM of Fe2+. However the rod type electrode
EF reactor could not be operated at electric currents greater than 0.8A/L due to the
limited voltage that the power supply can generate. The effect of initial aniline
concentration on aniline degradation was determined by varying the aniline concentration
from 2.5mM, 5mM, 10mM, 15mM and 22.5mM using 58mM of H2O2, 1.07mM of Fe2+
and a constant applied electric current of 0.8A/L.

Degradation experiments of a high initial aniline concentration with a 10,000ppm


COD was conducted using 640mM of H2O2, 11.85mM of Fe2+ and 0.8A/L of electric

16
current. Fe2+ regeneration experiments were conducted using 500ppm of Fe3+ at an initial
pH of 2. Figure 3-2 shows the summary procedure for the conduct of the experiments.

Prepare aniline Assemble electrode


solution in the reactor and power supply
vessel connections

Adjust pH to 3.2 using


sulfuric acid solution

Add determined amount


of Fe2+ and dissolve

Get samples for H2O2, Fe2+, Add determined amount of


aniline and organic acid H2O2 while simultaneously
analysis at the determined time turning on the power supply
intervals

Figure 3-2: Experimental procedure summary flowchart

3.4 Sampling and Laboratory Analyses

Samples were taken at determined time intervals of every 0, 2, 5, 10, 30, and 60
minutes for laboratory analysis. Samples for aniline analyses were first added into a 0.1N
NaOH solution to stop the Fenton reaction and for dilution. The samples were first
filtered using Whatman glass filter with pore size of 0.45 µm before injection into the
Gas Chromatograph equipment.

17
Laboratory analysis conducted for the samples followed the standard methods.
H2O2 analysis was conducted using iodometric titration method, closed reflux titrimetric
method for COD, permanganate titration method and phenanthroline method for Fe2+
analyses and azide modification method-dilution technique for BOD. Aniline was
analyzed using an HP 4890 Gas Chromatograph (GC) that was equipped with a flame
ionization detector and HP-5 column (0.53mm inside diameter and 15 m long). The GC
equipment used had injector and detector temperatures of 250 oC. Organic acids were
detected using DIONEX Ion Chromatograph equipped with an Ion Pac AS 11 analytical
column, 4 mm. ASRS-ULTRA suppressor using KOH as eluent at 1.0mL/min.

3.5 Statistical Analyses Methods

Statistical analyses used for calculating significant differences were the Paired-
Samples T-test and the Single Sample T-test using SPSS version 10.0 of SPSS Inc. 1989-
1999. Significant differences were concluded when the significance level value obtained
was less than 0.05 using 95% level of confidence. The Paired Samples T-test was used
when the significant difference between the two EF reactors at the same experimental
conditions was determined. Likewise the Single Sample T-test was used when the
significant difference between two parameters or indexes was determined at the same
experimental conditions.

3.6 Kinetic Modeling Method

Kinetic modeling was conducted by calculating the rate constants using the
aniline degradation data with respect to time. The data was fitted using the first order and
second order rate equations. The rate constant and coefficient of linearity was obtained by
plotting the data using Microcal(TM) Origin® Version 6.0 software of Microcal Software
Inc. The best fit was chosen when the coefficient of linearity was nearly equal to the
value of 1.

18
IV. RESULTS AND DISCUSSIONS

4.1 Aniline degradation using conventional Fenton and electro-Fenton processes

Aniline degradation using the conventional Fenton (CF) and electro-Fenton (EF)
processes was conducted to determine the difference in the treatment performance
between the two AOPs. Figure 4.1 (a) and (b) shows the aniline and COD remaining
ratios respectively using the CF and EF processes at 58mM of H2O2 and 0.27 mM of
Fe2+. At this experimental condition, the CF process had an aniline and COD removal
efficiency of 23.4% and 21.1% respectively. Aniline degradation from the CF process
stopped after five minutes of the reaction time as shown in Figure 4.1 (a). This
phenomenon was due to the competition of aniline degradation by products with
hydroxyl radicals as shown by the decreasing trend of COD after five minutes of the
reaction time.

1.0 1.0

0.8 0.8
Aniline remaining (C/Co)

COD remaining (C/Co)

0.6 0.6

0.4 0.4

0.2 0.2
Electro-Fenton Electro-Fenton
Conventional Fenton Conventional Fenton
0.0 0.0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
time (min) time (min)

(a) (b)
Figure 4-1: Effect of conventional Fenton and electro-Fenton processes on (a)
aniline degradation and (b) COD removal using [Fe2+] = 0.27mM; [H2O2] = 58mM.
Experimental condition: [aniline] = 10mM; IEF = 0.8A/L; initial pH = 3.2

19
Aniline degradation using the EF process was conducted by applying a constant
electric current of 0.8A/L at the same experimental condition. The EF process had an
aniline degradation efficiency and COD removal efficiency of 65.8% and 30.7%
respectively. Aniline degradation slowed down at time 30 minutes due to the competition
of aniline degradation by products with hydroxyl radicals as shown by the reduction of
COD in Figure 4.1 (b). The electro-Fenton process had a significantly higher aniline
degradation and COD removal efficiencies than the conventional Fenton process due to
the production of more hydroxyl radicals when excess H2O2 reacted with the electro
regenerated Fe2+.

Aniline degradation using a different experimental condition was also


investigated and is shown in Figure 4-2. Both of the CF and EF processes were operated
using 58mM of H2O2 and 1.07mM of Fe2+. The CF process had an aniline degradation
and COD removal efficiencies of 94.4% and 40.1% respectively. For the EF process,
increase in the Fe2+ resulted to aniline degradation and COD removal efficiencies of
99.5% and 45.9% respectively.

1.0 1.0
Electro-Fenton
0.8 Conventional Fenton 0.8
Aniline remaining (C/Co)

COD remaining (C/Co)

0.6 0.6

0.4 0.4

0.2 0.2
Electro-Fenton
Conventional Fenton
0.0 0.0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
time (min) time (min)

(a) (b)
Figure 4-2: Effect of conventional Fenton and electro-Fenton processes for (a)
aniline degradation and (b) COD removal using [Fe2+] = 1.07mM; [H2O2] = 58mM.
Experimental condition: [aniline] = 10mM; IEF = 0.8A/L; initial pH = 3.2

20
As shown in Figures 4-1 and 4-2, the treatment efficiencies of the CF and EF
processes were significantly different if the Fe2+ was low. At this operating condition the
EF process was obviously the best choice for aniline degradation because of its higher
aniline degradation and COD removal efficiencies. In addition to this, a study was
previously conducted on aniline degradation using 10mM of aniline, 230mM of H2O2
and 1.17mM of Fe2+. It was determined from the study that the EF process was more
effective than the CF process due to a 90% COD removal efficiency using step wise
addition of H2O2 (Lu 2003).

However if high Fe2+ concentration was applied, the treatment efficiency of the
CF process approaches that of the EF process. This phenomenon was also observed by
another study where the CF and EF processes were used for aniline degradation using an
initial aniline concentration of 10mM and 300mM of H2O2. Based on the study, the
aniline removal efficiency for the EF process decreased from 2.6 to 1.2 times of that of
the CF process when the Fe2+ was increased from 4mM to 18mM (Anotai 2006). Because
of this, choosing the best technology for aniline degradation at high Fe2+ concentrations is
now dependent on other operating factors like high inorganic sludge production and
presence of high residual H2O2 in the solution after treatment.

One advantage of the EF process is its ability to electro regenerate Fe2+ from Fe3+
at the cathode of the electrolytic system according to reaction (2.17). This ability reduces
sludge production since the high Fe2+ content solution from the EF process can be
recycled to treat another batch of aniline containing wastewater. Based on a previous
study, it was also determined that the treatment efficiency of the EF process using
recycled Fe2+ solution for five times had no detrimental effect on its treatment efficiency
(Tsai 2006). On the contrary, sludge production from the CF process is very high since
the Fe3+ rich solution would have to be disposed of after every treatment.

The CF process had a higher residual H2O2 at the experimental conditions used as
shown in Figure 4-3 (a) and (b). When 0.27mM of Fe2+ was used, the residual H2O2 for
the CF process was 1,440 mg/L while the EF process only had 450mg/L. Likewise at

21
1.07mM of Fe2+, the residual H2O2 for the CF process was 461mg/L while the EF process
had 18.6mg/L. Presence of high unreacted H2O2 in the treated solution from the CF
process was not economical due to wastage of a highly expensive chemical. Aside from
this, further treatment of the treated wastewater using biological processes will not be
feasible due to toxicity of high H2O2 concentration with microorganisms (Lu 1999).

2000 2000

1750 1750 Electro-Fenton


Conventional Fenton
1500 1500
H2O2 residual (mg/L)

H2O2 residual (mg/L)


1250 1250

1000 1000

750 750

500 500
Electro-Fenton
250 Conventional Fenton 250

0 0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
time (min) time (min)

(a) (b)
Figure 4-3: Residual H2O2 from aniline degradation using conventional Fenton and
electro-Fenton processes (a) [aniline] = 10mM; [Fe2+] = 0.27mM; H2O2 = 58mM; IEF
= 0.8A/L; initial pH = 3.2 and (b) [aniline] = 10mM; [Fe2+] = 1.07mM; H2O2 =
58mM; IEF = 0.8A/L; initial pH = 3.2

22
4.2 Fe2+ regeneration efficiency of the plate type electrode and rod type electrode EF
reactors

The Fe2+ regeneration efficiency of the two EF reactors was determined in the
study by conducting Fe3+ reduction experiments using 500ppm of Fe3+, an initial pH of 2
and a constant electric current of 0.8 A/L. Fe2+ regeneration efficiencies of the EF
reactors are shown in Figure 4-4. The rod type electrode EF reactor had a higher Fe2+
regeneration efficiency of 86% while the plate type electrode EF reactor had 51%. This
difference in the Fe2+ regeneration efficiencies between the two EF reactors was due to
the difference in the distance between the electrodes of the EF reactors. The plate type
electrode EF reactor had a shorter distance between the electrodes compared with the rod
type electrode EF reactor. Distance between the electrodes of an EF reactor affects Fe2+
regeneration due to different simultaneous reactions at the electrodes. Fe2+ would be
regenerated at the cathodes of the electrolytic system according to reaction (2.17).
However if the electrodes are placed too short, the electro regenerated Fe2+ would
immediately be oxidized at the anode according to reaction (4.1) (Zhang 2006).

Fe2+ Æ Fe3+ + e- (4.1)

100
plate type
rod type
Fe regeneration efficiency (%)

80

60

40

20
2+

0
0 10 20 30 40 50 60
time (min)

Figure 4-4: Fe2+ regeneration efficiency of the plate type electrode and rod type
electrode EF reactors. Experimental condition: [Fe3+] = 500ppm; I = 0.8A/L; pH = 2

23
4.3 Effect of H2O2, Fe2+, electric current and initial aniline concentration on the
aniline degradation efficiency using the plate type electrode and rod type electrode
EF reactors

The effect of H2O2, Fe2+, electric current and initial aniline concentration on
aniline degradation using the plate type electrode and rod type electrode EF reactors are
shown in Figures 4-5, 4-6, 4-7, and 4-8, respectively. The results showed that for both of
the EF reactors, aniline degradation rate was fast during the first 2 minutes of the reaction
then slowed down until the end of the reaction time. This high initial aniline degradation
rate was also observed when aniline degradation was conducted at different
concentrations of H2O2, Fe2+, electric current and initial aniline concentration. This high
initial aniline degradation rate was attributed to the reaction of aniline with hydroxyl
radicals that were formed during the first 2 minutes of the total reaction time according to
reaction (2.1).

1.0 1.0

2+
0.8 H2O2 = 0 mM; Fe = 0 mM 0.8 2+
H2O2 = 0 mM; Fe = 0 mM
Aniline remaining (C/Co)

Aniline remaining (C/Co)

H2O2 = 14.5 mM
H2O2 = 29.0 mM H2O2 = 14.5 mM
0.6 H2O2 = 58.0 mM 0.6 H2O2 = 29.0 mM
H2O2 = 87.0 mM H2O2 = 58.0 mM
H2O2 = 130 mM H2O2 = 87.0 mM
0.4 0.4 H2O2 = 130 mM

0.2 0.2

0.0 0.0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
time (min) time (min)

(a) (b)
Figure 4-5: Effect of H2O2 on aniline degradation using (a) plate type electrode and
(b) rod type electrode EF reactors. Experimental condition: [aniline] = 10mM;
[Fe2+] = 1.07mM; I = 0.8A/L; initial pH = 3.2

24
1.0 1.0
2+
2+
Fe = 0.27 mM Fe = 1.07 mM
2+
2+
Fe = 0.53 mM 0.8 Fe = 1.61 mM
0.8 2+
2+ Fe = 2.41 mM

Aniline remaining (C/Co)


Fe = 1.07 mM
Aniline remaining (C/Co)

2+
Fe = 1.61 mM
0.6 2+
Fe = 2.41 mM 0.6

0.4 0.4

0.2 0.2

0.0 0.0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
time (min) time (min)

(a) (b)
Figure 4-6: Effect of Fe2+ on aniline degradation using the (a) plate type electrode
and (b) rod type electrode EF reactors. Experimental condition: [aniline] = 10mM;
[H2O2] = 58mM; I = 0.8A/L; initial pH = 3.2

1.0 1.0
I = 0.20 A/L I = 0.20 A/L
I = 0.40 A/L I = 0.40 A/L
0.8 I = 0.80 A/L 0.8 I = 0.80 A/L
Aniline remaining (Co/C)
Aniline remaining (C/Co)

I = 1.20 A/L
I = 1.80 A/L
0.6 0.6

0.4 0.4

0.2 0.2

0.0 0.0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
time (min) time (min)

(a) (b)
Figure 4-7: Effect of electric current on aniline degradation using the (a) plate type
electrode and (b) rod type electrode EF reactors. Experimental condition: [aniline]
= 10mM; [H2O2] = 58mM; [Fe2+] = 1.07mM; initial pH = 3.2

25
1.0 1.0
Aniline = 2.50 mM Aniline = 2.50 mM
Aniline = 5.00 mM 0.8 Aniline = 5.00 mM
Aniline remaining (C/Co) 0.8
Aniline = 10.0 mM Aniline = 10.0 mM

Aniline remaining (C/Co)


Aniline = 15.0 mM Aniline = 15.0 mM
Aniline = 22.5 mM 0.6 Aniline = 22.5 mM
0.6

0.4 0.4

0.2 0.2

0.0 0.0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
time (min) time (min)

(a) (b)
Figure 4-8: Effect of initial aniline concentrations on aniline degradation using the
plate type electrode and rod type electrode EF reactors. Experimental condition:
[Fe2+] = 1.07mM; [H2O2] = 58mM; [Fe2+] = 1.07mM; initial pH = 3.2

Low aniline degradation rate after two minutes of the reaction time was due to
H2O2 reduction and competition of aniline degradation by products with hydroxyl
radicals. Aside from this, low aniline degradation after two minutes of the reaction time
was attributed to the reaction of aniline with non hydroxyl radical species and direct
anodic oxidation when no residual H2O2 was present in the reactor. Non hydroxyl radical
species like perhydroxyl radicals (HO2·), superoxide (O2·-) and hydroperoxide anions
(HO2-) were formed due to the presence of excess H2O2 and Fe2+ in the solution. These
non hydroxyl radicals were relatively weaker oxidants and were formed according to
reactions (2.4) to (2.8).

Degradation of aniline through direct anodic oxidation was attributed to the


production of adsorbed hydroxyl radicals at the anodes. These adsorbed hydroxyl radicals
were formed from the oxidation of water according to reaction (4.2) (Brillas 2004).

H2O Æ OHads· + H+ + e- (4.2)

26
Aniline degradation through direct anodic oxidation was also conducted and the
results are shown in Figure 4-5. Direct anodic oxidation was conducted using 10mM of
aniline at a constant electric current of 0.8A/L and without the addition of Fenton’s
reagents. Direct anodic oxidation resulted into an aniline degradation efficiency of 13%
for the plate type electrode and 18% for the rod type electrode EF reactors.

Aniline degradation efficiencies at different concentrations of H2O2, Fe2+, electric


current and initial aniline concentration using the plate type electrode and rod type
electrode EF reactors are shown in Tables 4-1, 4-2, 4-3, and 4-4 respectively. As shown
in Table 4-1, the aniline degradation efficiencies increased from 62.3% to 100% for the
plate type electrode EF reactor and 72.3% to 100% for the rod type electrode EF reactor
as the H2O2 concentration was increased from 14.5 mM to 130mM. This increase in the
aniline degradation efficiencies was due to the increase in the available H2O2 for the
production of more hydroxyl radicals when reacted with the electro regenerated Fe2+.
This phenomenon resulted into 100% aniline degradation efficiency for both of the EF
reactors at H2O2 concentrations greater than 58mM.

Table 4-1: Effect of H2O2 on the aniline degradation efficiency using the plate type
electrode and rod type electrode EF reactors
Aniline removal efficiency
H2O2
(%)
(mM)
Plate type electrode Rod type electrode
14.5 62.3 72.3
29.0 92.1 88.3
58.0 99.5 98.6
87.0 100 100
130 100 100
Experimental condition: [aniline] = 10mM; [Fe2+] = 1.07mM; I = 0.8A/L; pH = 3.2

However at 14.5 mM of H2O2, the rod type electrode EF reactor had an aniline
degradation efficiency of 72.3%, which was higher than the plate type electrode EF

27
reactor. This difference was attributed to the predominant effect of direct anodic
oxidation when the rod type electrode EF reactor was used at very low H2O2
concentrations as shown in Figure 4-5

On the contrary, at H2O2 concentrations of 29 mM and 58mM, the plate type


electrode had higher aniline degradation efficiencies of 92.1% and 99.5% respectively
than the rod type EF reactor, which were only 88.3% and 98.9% respectively. This
difference in the aniline removal efficiencies between the two EF reactors was due to the
different Fe2+ regeneration efficiencies of the EF reactors as shown in Figure 4-4. The rod
type electrode EF reactor had a higher Fe2+ regeneration efficiency. However presence of
an excess amount of electro regenerated Fe2+ from the rod type electrode EF reactor
could be inhibiting Fenton’s reaction due to the scavenging reactions with hydroxyl
radicals according to reaction (2.9), which would then result into lower aniline removal
efficiencies. Hydroxyl radical scavenging reactions of excess Fe2+ associated with Fenton
processes was also found in other studies. This phenomenon resulted into optimum Fe2+
concentrations for a specific experimental condition (Dutta 2003; Trapido 2003).

Aniline removal efficiencies using 58mM of H2O2 and 10mM of aniline at


different Fe2+ concentrations are shown in Table 4-2. Results showed that as the Fe2+
concentration was increased from 0.27mM to 2.41mM for the plate type electrode EF
reactor, the aniline degradation efficiency increased from 65.8% to 100%. While the
aniline degradation efficiency for the rod type electrode EF reactor also increased from
98.6% to 100% as the Fe2+ was increased from 1.07mM to 2.41mM. This phenomenon
was due to the increase in the available Fe2+ at the start of the reaction time that would
produce more hydroxyl radicals when reacted with H2O2. Both of the EF reactors had an
aniline degradation efficiency of 100% at Fe2+ concentrations greater than 1.61mM.
However at 1.07mM of Fe2+, the rod type electrode EF reactor had lower aniline
degradation efficiency which could be attributed to the hydroxyl radical scavenging
reactions of excess electro regenerated Fe2+ with hydroxyl radicals according to reaction
(2.9).

28
Table 4-2: Effect of Fe2+ on the aniline degradation efficiency using the plate type
electrode and rod type electrode EF reactors
Aniline removal efficiency
Fe2+
(%)
(mM)
Rod type electrode Plate type electrode
0.27 --- 65.8
0.53 --- 91.0
1.07 98.6 99.5
1.61 100 100
2.41 100 100
Experimental condition: [aniline] = 10mM; [H2O2] = 58mM; I = 0.8A/L; pH = 3.2

Aniline degradation using the rod type EF reactor was not carried out at Fe2+
concentrations lower than 1.07mM because the required electric current of 0.8A/L could
not be achieved due to the decrease in the conductivity of the solution. Because of this
different electric current application was also investigated in the study to determine its
effect on aniline degradation.

The electric current was varied from 0.20 A/L to 1.8 A/L for the plate type
electrode EF reactor and 0.20A/L to 0.80A/L for the rod type electrode EF reactor. The
rod type electrode EF reactor cannot be operated at electric currents higher than 0.8A/L
due to the limitations of the power supply used. Aniline degradation efficiencies at
different electric currents using the pate type electrode and rod type electrode EF reactors
are shown in Table 4-3. The results showed that as the electric current was increased
from 0.20A/L to 1.80A/L for the plate type electrode EF reactor, the aniline degradation
efficiency increased from 94.7% to 99.8%. Likewise as the electric current was increased
from 0.20A/L to 0.40A/L for the rod type electrode EF reactor, the aniline degradation
efficiency also increased from 97.94% to 99.4%. This increase in the aniline degradation
efficiencies was due to the increase in the production of electro regenerated Fe2+ at the
cathode as the electric current was increased (Zhang 2006). However as the electric
current was increased to 0.8A/L for the rod type electrode EF reactor, no further effect

29
was observed on the aniline degradation efficiency. This was due to the presence of
excess electro regenerated Fe2+.

As also shown in Table 4-3, the rod type electrode EF reactor had higher aniline
degradation efficiencies at electric currents of 0.20A/L to 0.40A/L. This phenomenon
was due to lower Fe2+ regeneration efficiency of the plate type electrode EF reactor at
these applied electric currents that resulted to an insufficient amount of Fe2+ for the
production of more hydroxyl radicals.

Table 4-3: Effect of electric current on the aniline degradation efficiency using the
plate type electrode and rod type electrode EF reactors
Aniline removal efficiency
Electric current
(%)
(A/L)
Plate type electrode Rod type electrode
0.20 94.7 97.9
0.40 96.9 99.4
0.80 99.4 98.6
1.20 99.5 ---
1.80 99.8 ---
Experimental condition:[aniline] = 10mM; [Fe2+] = 1.07mM; [H2O2] = 58mM;pH = 3.2

The aniline degradation efficiencies at different initial aniline concentrations are


shown in Table 4-4. Degradation of different initial aniline concentrations were
conducted using 58mM of H2O2 and 1.07mM of Fe2+ at a constant electric current of
0.8A/L. Initial aniline concentrations were varied from 2.50mM to22.5mM for both of
the EF reactors.

As shown in Table 4-4, aniline degradation efficiencies decreased from 100% to


87.2% for the plate type electrode EF reactor and 100% to 77.2% for the rod type
electrode EF reactor as the aniline concentration was increased from 2.50mM to 22.5mM.

30
This decrease in the initial aniline degradation rates and aniline removal efficiencies was
due to the insufficient amount of the Fenton reagents for aniline degradation.

As also shown in Table 4-4, the rod type electrode EF reactor had lower aniline
degradation efficiencies. This was due to the scavenging reactions of excess electro
regenerated Fe2+ with hydroxyl radical according to reaction (2.9).

Table 4-4: Effect of initial aniline concentration on the aniline degradation


efficiency using the plate type electrode and rod type electrode EF reactors
Aniline removal efficiency
Aniline
(%)
(mM)
Plate type electrode Rod type electrode
2.50 100 100
5.00 100 100
10.0 99.5 98.6
15.0 98.6 97.7
22.5 87.2 77.2
Experimental condition: [H2O2] = 58mM; [Fe2+] = 1.07mM; I = 0.8A/L; pH = 3.2

31
4.4 Effect of H2O2, Fe2+, electric current and initial aniline concentration on the
initial aniline degradation rate using the plate type electrode and rod type electrode
EF reactors.

Information on the effects of H2O2, Fe2+, electric current and initial aniline
concentrations on the initial aniline degradation rate was important since this rate was
attributed to the reaction of aniline with hydroxyl radicals and would therefore aid on
choosing possible options of achieving higher treatment efficiencies. The initial aniline
degradation rate was calculated using the amount of aniline degraded during the first two
minutes of the reaction time.

The effect of H2O2, Fe2+, electric current and initial aniline concentration on the
initial aniline degradation rates using the plate type and rod type electrode EF reactors are
shown in Tables 4-5, 4-6, 4-7 and 4-8. When the H2O2 concentration was increased from
14.5mM to 87mM, the initial aniline degradation rate increased from 2.69 mM min-1 to
4.19 mM min-1 for the plate type electrode EF reactor and 3.09 mM min-1 to 4.08 mM
min-1 for the rod type electrode EF reactor. This increase in initial aniline degradation
rate was due to the increase in the available H2O2 for the production of hydroxyl radicals
when reacted with Fe2+ according to reaction (2.1).

Table 4-5: Effect of H2O2 on initial aniline degradation rate using the plate type
electrode and rod type electrode EF reactors
Initial aniline degradation rate
H2O2
(mM min-1)
(mM)
Plate type electrode Rod type electrode
14.5 2.69 3.09
29.0 3.16 3.42
58.0 3.20 3.82
87.0 4.19 4.08
130 4.17 3.97
Experimental condition: [aniline] = 10mM, [Fe2+] = 1.07mM, I = 0.8A/L, pH = 3.2

32
However the change in the initial aniline degradation rate was not significant
when the H2O2 concentration was further increased to 130 mM. This phenomenon was
due to scavenging reactions of excess H2O2 with hydroxyl radicals according to reaction
(2.4) and Fe3+ according to reaction (2.11). The difference in initial aniline degradation
rates between the two EF reactors was determined to be not significant.

The effect of Fe2+ on the initial aniline degradation rate is shown in Table 4-6.
The initial aniline degradation rate increased from 1.44 mM min-1 to 4.2 mM min-1 as the
Fe2+ concentration was increased from 0.27mM to 1.61mM for the plate type electrode
EF reactor and 3.82 mM min-1 to 4.25 mM min-1 for the rod type electrode EF reactor as
the Fe2+ concentration was increased from 1.07mM to 2.41mM.

This increase in initial aniline degradation rates was due to the increase in the
available initial Fe2+ needed for the production of more hydroxyl radicals when reacted
with H2O2. However further increase of Fe2+ to 2.41mM had no further significant effect
on the initial degradation rate due to the scavenging reactions of excess Fe2+ with
hydroxyl radicals according to reaction (2.9).

Table 4-6: Effect of Fe2+ on the initial aniline degradation rate using the plate type
electrode and rod type electrode EF reactors
Initial aniline degradation rate
Fe2+
(mM min-1)
(mM)
Plate type electrode Rod type electrode
0.27 1.44 ---
0.53 1.47 ---
1.07 3.2 3.82
1.61 4.2 4.25
2.41 4.64 4.46
Experimental condition: [aniline] = 10mM; [H2O2] = 58mM; I = 0.8A/L, pH = 3.2

33
The effect of electric current on the initial aniline degradation rate is shown in
Table 4-7. The initial aniline degradation rate increased from 2.98 mM min-1 to 3.74 mM
min-1 as the electric current was increased from 0.20A/L to 1.80A/L for the plate type
electrode EF reactor. For the rod type electrode EF reactor, the change in the initial
aniline degradation was not significant due to scavenging reactions of excess electro
regenerated Fe2+ according to reaction (2.9). Results also showed that the difference in
the initial aniline degradation rates between the two EF reactors at different electric
current applications were not significant.

Table 4-7: Effect of electric current on the initial aniline degradation rate using the
plate type electrode and rod type electrode EF reactors
Initial aniline degradation rate
Electric current
(mM min-1)
(A/L)
Plate type electrode Rod type electrode
0.20 2.98 3.33
0.40 3.14 3.11
0.80 3.2 3.82
1.20 3.66 ---
1.80 3.74 ---
Experimental condition: [aniline]=10mM, [H2O2]=58mM, [Fe2+]=1.07mM, pH = 3.2

The effect of different initial aniline concentrations on the initial aniline


degradation rate is shown in Table 4-8. The initial aniline degradation rate decreased
from 5.00 mM min-1 to 1.68 mM min-1 for the plate type electrode EF reactor and
5.00mM min-1 to 0.68mM min-1 for the rod type electrode EF reactor as the initial aniline
concentration was increased from 2.50mM to 22.5 mM. The decrease in the initial aniline
degradation rates was attributed to the insufficient amount of Fenton’s reagents for the
production of hydroxyl radicals during the first two minutes of the total reaction time.

For both of the EF reactors, the difference in the initial aniline degradation rates
was also not significant.

34
Table 4-8: Effect of initial aniline concentration on initial aniline degradation rate
and aniline removal efficiency using plate type electrode and rod type electrode EF
reactors
Aniline Initial aniline degradation rate
(mM min-1)
(mM) Plate type electrode Rod type electrode
2.50 5.00 5.00
5.00 4.50 3.70
10.0 3.20 3.52
15.0 3.00 3.32
22.5 1.68 0.68
Experimental condition: I = 0.8A/L; [H2O2] = 58mM; [Fe2+] = 1.07mM; pH = 3.2

35
4.5 Effect of H2O2, Fe2+, electric current, initial aniline degradation concentration on
the second order aniline degradation rate constant using the plate type electrode
and rod type electrode EF reactors

The kinetic model for aniline degradation and its response to different
concentrations of H2O2, Fe2+, electric current and initial aniline concentrations were also
determined in the study. Aniline degradation for both of the EF reactors followed the
second order behavior and the effect of H2O2, Fe2+, electric current and initial aniline
concentrations on aniline degradation rate constants are shown in Figures 4-9, 4-10, 4-11
and 4-12 respectively. Data on aniline degradation with respect to time on the effects of
H2O2, Fe2+, electric current and initial aniline concentration from Figures 4-5 to 4-8
were used to calculate the rate constants as shown in Appendix A.

The effect of H2O2 on the aniline degradation rate constant is shown in Figure 4-
9. The rate constants increased from 14.1x10-2 M-1 min-1 to 304 x10-2 M-1 min-1 and 21.5
x10-2 M-1 min-1 to 219 x10-2 M-1 min-1 for the plate type and rod type electrode EF
reactors respectively as the H2O2 concentration was increased from 14.5mM to 130mM.

350
plate type
300 rod type
rate constant, k (x10 M min )
-1

250
-1
-2

200

150

100

50

0
0 20 40 60 80 100 120 140
H2O2 (mM)

Figure 4-9: Effect of H2O2 on the second order aniline degradation rate constant
using the plate type electrode and rod type electrode EF reactors. Experimental
condition: [aniline] = 10mM; [Fe2+] = 1.07mM; I = 0.8A/L; initial pH = 3.2

36
This increase in rate constants was due to the presence of excess H2O2 forming
more hydroxyl radicals when reacted with the electro regenerated Fe2+. As also shown in
Figure 4-9, the rod type electrode EF reactor had lower rate constants at H2O2
concentrations higher than 29mM. This difference was due to higher hydroxyl radical
competition of aniline degradation by products when the rod type electrode EF reactor
was used. At 14.5mM and 29mM of H2O2, the rod type and plate type electrode EF
reactors have the same rate constants due to the insufficient amount of H2O2 for further
aniline degradation.

The kinetic model for aniline degradation at different Fe2+ concentrations using
the plate type electrode and rod type electrode EF reactors is shown in Figure 4-10. The
second order rate constant increased from 21.5 x 10-2 M-1 min-1 to 429 x 10-2 M-1 min-1 as
the Fe2+ concentration was increased from 0.27mM to 2.41mM for the plate type
electrode EF reactor. Likewise for the rod type electrode EF reactor, the second order rate
constant also increased from 50.7 x 10-2 M-1 min-1 to 318 x 10-2 M-1 min-1 as the Fe2+
concentration was increased from 1.07mM to 2.41mM.

500
plate type
rod type
rate constant, k (x10 M min )

400
-1
-1

300
-2

200

100

0
0.0 0.5 1.0 1.5 2.0 2.5
2+
Fe (mM)

Figure 4-10: Effect of Fe2+ on the second order aniline degradation rate constant
using the plate type electrode and rod type electrode EF reactors. Experimental
conditions: [aniline] = 10mM; [H2O2] = 58mM; I = 0.8A/L; initial pH = 3.2

37
This increase in the rate constants was attributed to the increase in the production
of hydroxyl radicals when the initial Fe2+ for the reaction with H2O2 was increased. As
also shown in Figure 4-10, the rod type electrode EF reactor had lower aniline
degradation rate constants at all Fe2+ concentrations due to higher presence of scavenging
reactions of excess electro regenerated Fe2+.

The effect of electric current on the aniline degradation rate constant is shown in
Figure 4-11. For the plate type electrode EF reactor, the rate constant increased from 21.5
x 10-2 M-1 min-1 to 299 x 10-2 M-1 min-1 as the electric current was increased from
0.20A/L to 1.80A/L. Likewise, the rate constant for the rod type electrode EF reactor
increased from 51.9 x 10-2 M-1 min-1 to 101 x 10-2 M-1 min-1 as the electric current was
increased from 0.20A/L to 0.40A/L. However as the electric current was further
increased to 1.8A/L and 0.8A/L for the plate type electrode and rod type electrode EF
reactors respectively, the aniline degradation rate constants decreased to 253 x 10-2 M-1
min-1 and 68.2 x 10-2 M-1 min-1 respectively.

350
plate type
300
rod type
rate constant, k (x10 M min )
-1

250
-1
-2

200

150

100

50

0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
electric current (A/L)

Figure 4-11: Effect of electric current on the second order aniline degradation rate
constant using the plate type electrode and rod type electrode EF reactors.
Experimental condition: [aniline] = 10mM; [H2O2] = 58mM; [Fe2+] = 1.07mM;
initial pH = 3.2

38
This decrease in the aniline degradation rate constants was due to the scavenging
reactions of excess electro regenerated Fe2+. The decrease was also attributed to increased
competitive reactions at the electrodes like production of O2 and H2 at the anode and
cathode respectively according to reactions (4.3) and (4.4) (Zhang 2006).

2H2O2 Æ 4H+ + O2 + 4e- (4.3)


2H+ + e- Æ H2 (4.4)

The effect of different initial aniline concentrations on the aniline degradation rate
constant is shown in Figure 4-12. The aniline degradation rate constants for both of the
EF reactors decreased as the initial aniline concentration was increased from 2.5mM to
22.5mM. However the rod type electrode EF reactor had lower rate constants at initial
aniline concentrations of 2.5mM and 5mM due to the scavenging reactions of excess
electro regenerated Fe2+. However at higher aniline concentrations both EF reactors have
the same aniline degradation rate constants.

500
plate type
rod type
rate constant, k (x10 M min )

400
-1
-1

300
-2

200

100

0
0 5 10 15 20 25
Aniline (mM)

(a) (b)
Figure 4-12: Effect of initial aniline concentration on the second order aniline
degradation rate constant using the plate type electrode and rod type electrode EF
reactors. Experimental condition: I = 0.8A/L; [H2O2] = 58mM; [Fe2+] = 1.07mM;
initial pH = 3.2

39
4.6 Effect of H2O2, Fe2+, electric current, initial aniline concentration on the COD
removal efficiency using the plate type electrode and rod type electrode EF reactors

The effects of H2O2, Fe2+, electric current and initial aniline concentrations on
COD removal efficiencies were also determined in the study and are shown in Tables 4-
9, 4-10, 4-11 and 4-12, respectively.

The effect of H2O2 on the COD removal is shown in Table 4-9. COD removal
efficiencies increased from 31.1% to 60.2% and 18.8% to 61.9% for the plate type
electrode and rod type electrode EF reactors respectively as the H2O2 concentration was
increased from 14.5mM to 130mM. This increase in COD removal efficiencies was due
to the increase in available H2O2 for the production of hydroxyl radicals. As also shown
in Table 4-9, the rod type electrode EF reactor had higher COD removal efficiencies at
H2O2 concentrations of 87 mM and 130mM which was 53.3% and 61.9% respectively.
This difference in COD removal efficiencies was due to the difference in the Fe2+
regeneration abilities between the two EF reactors and the higher competition of aniline
degradation by products with the hydroxyl radicals as determined from the effect of H2O2
on the second order aniline degradation rate constant.

Table 4-9: Effect of H2O2 on the COD removal efficiency using the plate type
electrode and rod type electrode EF reactors
COD removal efficiency
H2O2
(%)
(mM)
Plate type electrode Rod type electrode
14.5 31.1 18.8
29.0 33.5 22.3
58.0 45.9 40.9
87.0 47.9 53.2
130 60.2 61.9
2+
Experimental condition: [aniline] = 10mM, [Fe ] = 1.07mM, I = 0.8A/L, pH = 3.2

40
Therefore at higher H2O2 concentrations, excess H2O2 are available for the
regenerated Fe2+ to produce more hydroxyl radicals. However, the high Fe2+ regeneration
capacity of the rod type electrode EF reactor will yield lower COD removal efficiencies
at H2O2 concentrations lower than 87 mM due to scavenging reactions of regenerated
Fe2+ with hydroxyl radicals according to reaction (2.9).

COD removal efficiencies at different Fe2+ concentrations using the plate type
electrode and rod type electrode EF reactors are shown in Table 4-10. As the Fe2+
concentration was increased from 0.27mM to 1.61mM for the plate type electrode EF
reactor, the COD removal efficiency increased from 30.7% to 46.7%. Likewise as the
Fe2+ concentration was increased from 1.07mM to 1.61mM for the rod type electrode EF
reactor, the COD removal efficiency slightly increased from 40.9% to 43.6%.

Table 4-10: Effect of Fe2+ on the COD removal efficiency using the plate type
electrode and rod type electrode EF reactors
COD removal efficiency
Fe2+
(%)
(mM)
Plate type electrode Rod type electrode
0.27 30.7 ---
0.53 39.9 ---
1.07 45.9 40.9
1.61 46.7 43.6
2.41 43.9 40.9
Experimental condition: [aniline] = 10mM, [H2O2] = 58mM, I = 0.8A/L, pH = 3.2

However for both of the EF reactors, further increase of Fe2+ to 2.41mM resulted
into a decrease of the COD removal efficiency to 43.9% and 40.9% for the plate type
electrode and rod type electrode EF reactors respectively. This decrease was due to the
scavenging reactions of excess Fe2+ with hydroxyl radicals according to reaction (2.9).
Aside from this, the rod type electrode EF reactor had lower COD removal efficiencies
due to presence of excess electro regenerated Fe2+.

41
COD removal efficiencies at different applied electric current are shown in Table
4-11. COD removal efficiencies increased from 37.3% to 44.8% for the plate type
electrode EF reactor as the electric current was increased from 0.20A/L to 1.20A/L. For
the rod type electrode EF reactor, the COD removal efficiency also increased from 42.2%
to 43.28% as the electric current was increased from 0.20A/L to 0.80A/L. However for
the plate type electrode EF reactor, further increase of the electric current to 1.8A/L had
no further effect on the COD removal efficiency. This was due to the increase in the
scavenging reactions of the excess electro regenerated Fe2+ and the increase in the
competitive reactions at the electrodes according to reaction (4.3) and (4.4).

Table 4-11: Effect of electric current on the COD removal efficiency using the plate
type electrode and rod type electrode EF reactors
COD removal efficiency
Electric Current
(%)
(A/L)
Plate type electrode Rod type electrode
0.20 37.3 42.2
0.40 43.8 43.3
0.80 45.9 40.9
1.20 44.8 ---
1.80 43.4 ---
Experimental condition: [aniline] = 10mM; [H2O2] = 58mM; I = 0.8A/L; pH = 3.2

The effect of different initial aniline concentrations on the COD removal


efficiencies is shown in Table 4-12. The COD removal efficiency decreased from 57% to
33.5% for the plate type electrode EF reactor and 76.1% to 30.5% for the rod type
electrode EF reactor as the initial aniline concentration was increased from 2.50mM to
22.5mM.

As also shown in Table 4-12, the rod type electrode EF reactor had higher
competitions of aniline degradation by product with hydroxyl radicals at initial aniline
concentrations lower than 10mM. This was due to higher COD removal efficiency than

42
the plate type electrode EF reactor but had lower aniline degradation efficiency as
determined previously from the effect of initial aniline concentrations on the aniline
degradation efficiencies.

At initial aniline concentrations greater than 10mM, the difference in the COD
removal efficiencies was not significant between the two EF reactors.

Table 4-12: Effect of initial aniline concentration on the COD removal efficiency
using the plate type electrode and rod type electrode EF reactors
COD removal efficiency
Aniline (mM) (%)
Plate type electrode Rod type electrode
2.50 57.0 76.1
5.00 56.7 62.9
10.0 45.9 40.9
15.0 34.5 32.1
22.5 33.5 30.5
Experimental condition: [aniline] = 10mM; [H2O2] = 58mM; I = 0.8A/L; pH = 3.2

43
4.7 Effect of H2O2, Fe2+, electric current, initial aniline concentration on the H2O2
efficiency for aniline and COD removal using the plate type electrode and rod type
electrode EF reactors.

The H2O2 efficiency for aniline and COD removal was determined in the study
since it was an important index that would aid in achieving the optimum usage of H2O2
for the production of hydroxyl radicals. Obtaining the optimum usage of H2O2 was
important since H2O2 was the most expensive compound used in the EF process. In
addition to this, H2O2 efficiency was also an index that would determine presence of
scavenging reactions of different species with hydroxyl radicals.

The H2O2 efficiency for aniline removal was calculated using the amount of H2O2
consumed for the amount of aniline or COD removed. Theoretically, the highest H2O2
efficiency of 100% for aniline removal would mean that 1 mol of aniline was removed by
1 mol of H2O2. The H2O2 efficiency for COD removal was calculated using equation (1)
(Zhang 2006)

η = ∆COD (mg/L) x 100 (1)


available O2 (mg/L)

where the available O2 is the theoretical reactive oxygen in the amount of H2O2
consumed with respect to the amount of COD removed.

The effect of H2O2, Fe2+, electric current and initial aniline concentrations on the
H2O2 efficiency on aniline and COD removal are shown in Tables 4-13, 4-14, 4-15, and
4-16 respectively.

The effect of H2O2 on the H2O2 efficiency for aniline and COD removal is shown
in Table 4-13. The H2O2 efficiency for aniline removal at 14.5mM of H2O2 was 42.9%
and 49.9% for the plate type electrode and rod type electrode EF reactors, respectively.
This means that not all of the H2O2 consumed were used to degrade aniline only. The

44
H2O2 consumed could be used for the degradation of intermediates or by scavenging
reactions.

However the H2O2 efficiencies for COD removal at 14.5mM of H2O2 were high,
which was 307% and 186% for the plate type electrode and rod type electrode EF
reactors respectively. H2O2 efficiencies higher than 100% were possible in this study
since aniline degradation and COD removal was not only attributed to Fenton’s reactions.

As the H2O2 was increased to 130mM, the H2O2 efficiencies for aniline and COD
removal further decreased for both of the plate type and rod type electrode EF reactors.
This decrease in the H2O2 efficiency was due to the scavenging reactions of excess H2O2
with hydroxyl radicals according to reaction (2.4). As also shown in Table 4-13, both of
the EF reactors had the same H2O2 efficiencies for aniline removal. However at low H2O2
concentration of 14.5mM, the rod type electrode EF reactor had a slightly higher H2O2
efficiency for aniline removal due to the higher aniline degradation efficiency caused by
the added effect of direct anodic oxidation.

Table 4-13: Effect of H2O2 on the H2O2 efficiencies for aniline and COD removal
using the plate type electrode and rod type electrode EF reactors
H2O2 efficiency for aniline H2O2 efficiency for COD
removal removal
H2O2
(%) (%)
(mM)
Plate type Rod type Plate type Rod type
electrode electrode electrode electrode
14.5 42.9 49.9 307 186
29.0 31.7 30.5 165 110
58.0 17.3 17.0 114 101
87.0 12.0 12.8 82.2 98.3
130 9.93 10.6 85.6 94.6
2+
Experimental condition: [aniline] = 10mM, [Fe ] = 1.07mM, I = 0.8A/L, pH = 3.2

45
In addition to this, the rod type electrode EF reactor had lower H2O2 efficiency for
COD removal at low H2O2 concentrations due to the presence of scavenging reactions of
excess electro regenerated Fe2+.

The effect of Fe2+ on the H2O2 efficiency for aniline and COD removal are shown
in Table 4-14. The H2O2 efficiency for aniline and COD removal decreased from 58.7%
to 7.69% and 191% to 23.6% respectively as the Fe2+ concentrations was increased from
0.27mM to 2.41mM for the plate type electrode EF reactor. Likewise for the rod type
electrode EF reactor, the H2O2 efficiency for aniline and COD removal also decreased
from 17.0% to 7.69% and 49.3% to 22.0% respectively. This decrease in the H2O2
efficiency was due to the scavenging reactions of excess Fe2+ with hydroxyl radicals
according to reaction (2.9) as the Fe2+ concentration was increased.

As also shown in Table 4-14, the difference in the H2O2 efficiencies for aniline
and COD removal between the two EF reactors was not significant at different Fe2+
concentrations.

Table 4-14: Effect of Fe2+ on the H2O2 efficiency for aniline and COD removal using
the plate type electrode and rod type electrode EF reactors
H2O2 efficiency for aniline H2O2 efficiency for COD
removal removal
Fe2+
(%) (%)
(mM)
Plate type Rod type Plate type Rod type
electrode electrode electrode electrode
0.27 58.7 --- 191 ---
0.53 36.3 --- 111 ---
1.07 17.3 17.0 55.9 49.3
1.61 11.5 11.5 37.6 35.1
2.41 7.69 7.69 23.6 22.0
Experimental condition: [aniline] = 10mM, [H2O2] = 58mM, I = 0.8A/L, pH = 3.2

46
The H2O2 efficiency for aniline and COD removal at different electric current
applications are shown in Table 4-15. The H2O2 efficiency for aniline and COD removal
decreased from 73.1% to 7.71% and 412% to 48% respectively as the electric current was
increased from 0.20A/L to 1.8A/L for the plate type electrode EF reactor. Likewise for
the rod type electrode EF reactor, the H2O2 efficiency for aniline and COD removal also
decreased from 71.6% to 17.0% and 441% to 100% respectively when the electric current
was increased from 0.20A/L to 0.80A/L. This decrease in the H2O2 efficiency was due to
the presence of excess electro regenerated Fe2+ that was inhibiting Fenton reactions by
scavenging the hydroxyl radicals according to reaction (2.9). This decrease in
degradation efficiencies was also attributed to the increase in competitive reactions at the
electrodes such as the production of O2 and H2 at the anode and cathode respectively.

As also shown in Table 4.15, both of the EF reactors had nearly the same H2O2
efficiencies for aniline and COD removal.

Table 4.-15: Effect of electric current on the H2O2 efficiency for aniline and COD
removal using the plate type electrode and rod type electrode EF reactors
H2O2 efficiency for aniline H2O2 efficiency for COD
Electric removal removal
Current (%) (%)
(A/L) Plate type Rod type Plate type Rod type
electrode electrode electrode electrode
0.20 73.1 71.6 412 441
0.40 35.5 36.0 229 226
0.80 17.3 17.0 114 100
1.20 11.5 --- 73.8 ---
1.80 7.31 --- 48.0 ---
Experimental condition: [aniline] = 10mM; [H2O2] = 58mM; I = 0.8A/L; pH = 3.2

47
The effect of initial aniline concentration on the H2O2 efficiency for aniline and
COD removal are shown in Table 4-16. The H2O2 efficiency for aniline and COD
removal for the plate type electrode EF reactor decreased from 69.0% to 6.71% and
563% to 36.9% respectively as the initial aniline concentration was increased from
2.50mM to 22.5mM. Likewise for the rod type electrode EF reactor, the H2O2 efficiency
for aniline and COD removal also decreased from 71.4% to 6.04% and 777% to 34.2%
respectively. This decrease in the H2O2 efficiencies was due to the decrease in the aniline
and COD removal efficiencies as determined from the effect of initial aniline
concentration on aniline and COD removal efficiencies.

As also shown in Table 4-16, the difference on the H2O2 efficiencies for aniline
and COD removal between the two EF reactors was not significant.

Table 4-16: Effect of initial aniline concentration on the H2O2 efficiency for aniline
and COD removal using the plate type electrode and rod type electrode EF reactors
H2O2 efficiency for aniline H2O2 efficiency for COD
removal removal
Aniline
(%) (%)
(mM)
Plate type Rod type Plate type Rod type
electrode electrode electrode electrode
2.50 69.0 71.4 563 777
5.00 34.5 36.6 279 329
10.0 17.3 17.1 114 100
15.0 10.5 11.2 56.8 52.8
22.5 6.71 6.04 36.9 34.2
Experimental condition: [aniline] = 10mM; [H2O2] = 58mM; I = 0.8A/L; pH = 3.2

48
4.8 Effect of H2O2, Fe2+, electric current and initial aniline concentration on the
power consumption for aniline and COD removal using the plate type electrode and
rod type electrode EF reactors

The effect of H2O2, Fe2+, electric current and initial aniline concentration on the
power consumption for aniline and COD removal using the plate type electrode and rod
type electrode EF reactors were also determined in the study and are shown in Figures 4-
13, 4-14, 4-15 and 4-16 respectively. Power consumption for aniline and COD removal
was calculated using equation (2) (Brillas 2002).

Power (kWh/L) = V (V) * I (A) * t (hr) x [aniline]initial (or [COD]initial) (2)


vol (L) ∆aniline (or ∆COD)

where V is the average voltage for the total reaction time t and vol is the total volume of
solution treated.

The effect of H2O2 on power consumption for aniline and COD removal is shown
in Figure 4-13. The power consumption for aniline degradation and COD removal
decreased from 0.009kWh/L to 0.005kWh/L and 0.018kWh/L to 0.010kWh/L
respectively for the plate type electrode EF reactor as the H2O2 concentration was
increased from 14.5mM to 58mM. For the rod type electrode EF reactor the power
consumption for aniline degradation and COD removal decreased from 0.025kWh/L to
0.014kWh/L and 0.10kWh/L to 0.030kWh/L respectively when the H2O2 concentration
was increased from 14.5mM to 58mM. This decrease in power consumption was due to
the increase in aniline and COD removal efficiencies as the H2O2 concentration was
increased from 14.5mM to 58mM. However further increase of H2O2 to 87mM and
130mM had no further effect on power consumption since aniline and COD removal
efficiencies did not change significantly. As also shown in Figure 4-13, the power
consumption for aniline and COD removal for the rod type electrode EF reactor was
twice as much as the plate type electrode EF reactor. Likewise, COD removal requires
twice as much power than aniline removal.

49
Power consumption for aniline removal (KWh/L)
0.030

Power consumption for COD removal (KWh/L)


plate type 0.10 plate type
0.025 rod type rod type
0.08
0.020

0.06
0.015

0.04
0.010

0.005 0.02

0.000 0.00
0 20 40 60 80 100 120 140 0 20 40 60 80 100 120 140
H2O2 (mM) H2O2(mM)

(a) (b)
Figure 4-13: Effect of H2O2 on the power consumption for aniline and COD removal
using the plate type electrode and rod type electrode EF reactors. Experimental
condition: [aniline] = 10mM; [H2O2] = 58mM; I = 0.8A/L; initial pH = 3.2

The power consumption for aniline and COD removal at different Fe2+
concentrations using the plate type electrode and rod type electrode EF reactors are
shown in Figure 4-14 (a) and (b) respectively. The power consumption for aniline
degradation and COD removal decreased from 0.009kWh/L to 0.005kWh/L and
0.019kWh/L to 0.009kWh/L respectively for the plate type electrode EF reactor as the
Fe2+ concentration was increased from 0.27mM to 1.07mM. For the rod type electrode
EF reactor the power consumption for aniline degradation and COD removal decreased
from 0.014kWh/L to 0.012kWh/L and 0.034kWh/L to 0.029kWh/L respectively when the
Fe2+ concentration was increased from 1.07mM to 1.61mM. This decrease in power
consumption was due to the increase in the conductivity of the solution when more Fe2+
ions were added. An increase in conductivity resulted into lower voltage requirements at
constant electric current therefore lowering power consumption. Aside from this, power
consumption also decreased when aniline and COD removal efficiencies increased based
on equation (2). Because of this, increasing the Fe2+ concentration greater than 1.07mM

50
for the plate type EF reactor had no further effect on power consumption for aniline and
COD removal since the aniline and COD removal efficiencies decreased at these Fe2+
concentrations.
Power requirement for aniline removal (KWh/L)

0.040

Power requirement for COD removal (KWh/L)


0.014 plate plate
0.035 rod
rod
0.012
0.030
0.010
0.025
0.008
0.020
0.006 0.015
0.004 0.010
0.002 0.005

0.000 0.000
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0
2+ 2+
Fe (mM) Fe (mM)

(a) (b)
2+
Figure 4-14: Effect of Fe on the power consumption for aniline and COD removal
using the plate type electrode and rod type electrode EF reactors. Experimental
condition: [aniline] = 10mM; [H2O2] = 58mM; I = 0.8A/L; initial pH = 3.2

The effect of electric current on the power consumption for aniline and COD
removal using the plate type electrode and rod type electrode EF reactors are shown in
Figure 4-15 (a) and (b) respectively. The power consumption for aniline degradation and
COD removal increased from 0.003kWh/L to 0.007kWh/L and 0.006kWh/L to
0.017kWh/L respectively for the plate type electrode EF reactor as the electric current
was increased from 0.20A/L to 1.8A/L For the rod type electrode EF reactor, the power
consumption for aniline degradation and COD removal also increased from 0.005kWh/L
to 0.014kWh/L and 0.011kWh/L to 0.034kWh/L respectively when the electric current
was increased from 0.20A/L to 0.80A/L. Increase in power consumption was
significantly affected by the increase in the applied electric current rather than the aniline
degradation and COD removal efficiencies.

51
As also shown in Figure 4-15, the difference in the power consumption for the rod
type electrode and plate type electrode EF reactors also significantly increased from 1.7
times at 0.2A/L to 3.3 times at 0.8A/L. This increase in the difference in the power
consumption between the rod type electrode and plate type electrode EF reactors was due
to the higher decrease in the aniline and COD removal efficiencies for the rod type
electrode EF reactor at high electric current applications.
Power consumption for aniline removal (kWh/L)

0.016 0.040

Power consumption for COD removal (kWh/L)


0.014 plate 0.035 plate
rod rod
0.012 0.030

0.010 0.025

0.008 0.020

0.006 0.015

0.004 0.010

0.002 0.005

0.000 0.000
0.0 0.3 0.6 0.9 1.2 1.5 1.8 0.0 0.3 0.6 0.9 1.2 1.5 1.8
electric current (A/L) electric current (A/L)

(a) (b)
Figure 4-15: Effect of electric current on the power consumption for aniline and
COD removal using the plate type electrode and rod type electrode EF reactors.
Experimental condition: [aniline] = 10mM; [H2O2] = 58mM; [Fe2+] = 1.07mM;
initial pH = 3.2

The effect of different initial aniline concentration on power consumption for


aniline and COD removal is shown in Figure 4-16 (a) and (b) respectively. The power
consumption for aniline degradation slightly decreased from 0.006kWh/L to 0.005kWh/L
and 0.023kWh/L to 0.013kWh/L for the plate type electrode and rod type electrode EF
reactor respectively as the initial aniline concentration was increased from 2.50 mM to
22.5 mM. Decrease in power consumption for aniline removal was due to the increase in
the conductivity of the solution as the aniline concentration was increased. However this

52
phenomenon slightly decreases the power consumption for aniline removal for the plate
type EF reactor since the aniline removal efficiencies were low

In contrast, the power consumption for COD removal slightly increased from
0.010kWh/L to 0.130kWh/L for the plate type electrode EF reactor and 0.030kWh/L to
0.040kWh/L for the rod type electrode EF reactor. Power consumption for COD removal
slightly increases for both of the EF reactors due to the predominant effect of the
decrease in the COD removal efficiencies.
Power consumption for aniline removal (kWh/L)

0.028

Power consumption for COD removal (kWh/L)


0.049
plate type plate type
0.024 rod type 0.042 rod type

0.020 0.035

0.016 0.028

0.012 0.021

0.008 0.014

0.004 0.007

0.000 0.000
0 5 10 15 20 25 0 5 10 15 20 25
Aniline (mM) Aniline (mM)

(a) (b)
Figure 4-16: Effect of initial aniline concentration on the power consumption for
aniline and COD removal using the plate type electrode and rod type electrode EF
reactors. Experimental condition: I = 0.80A/L; [H2O2] = 58mM; [Fe2+] = 1.07mM;
initial pH = 3.2

53
4.9 Degradation of high initial aniline concentration

Aniline degradation using a very high initial aniline concentration having a COD
value of 10,000ppm was also investigated in the study. The aniline remaining and COD
remaining ratios from the experiment are shown in Figure 4-17 (a) and (b), respectively.
For both of the EF reactors, 100% of the aniline was removed at time 2 minutes of the
reaction. Likewise, the COD removal efficiency for both of the EF reactors was 86% at
the end of the reaction time. Both of the EF reactors had the same aniline and COD
removal efficiencies at this initial aniline concentration since it was shown in the results
from the effect of initial aniline concentration on the aniline and COD removal
efficiencies that both of the EF reactors had the same treatment performance at higher
initial aniline concentrations.

1.0 1.0
plate type plate type
rod type rod type
0.8 0.8
Aniline remaining (C/Co)

COD remaining (C/Co)

0.6 0.6

0.4 0.4

0.2 0.2

0.0 0.0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
time (min) time (min)

(a) (b)
Figure 4-17: Aniline and COD remaining ratios from degradation of 10,000ppm
COD of aniline using the plate type electrode and rod type electrode EF reactors.
Experimental condition: [H2O2] = 640mM; [Fe2+] = 11.9mM; initial pH = 3.2

The change in the BOD and toxicity of the aniline solution was also determined in
the study and is shown in Figure 4-18 (a) and (b) respectively. The initial BOD and
toxicity of the aniline solution was determined to be both at 0mg/L. This means that the

54
10,000ppm COD of aniline was initially not biodegradable and was highly toxic to
microorganisms.

0.25

300
0.20
250
BOD (mg/L)

200 0.15

BOD/COD
150
0.10
100
0.05
50

0 0.00
rod type EF plate type EF rod type EF plate type EF

(a) (b)
Figure 4-18: BOD and toxicity tests on treated high concentration aniline solution
using the plate type electrode and rod type electrode EF reactors. Experimental
condition: [H2O2] = 640mM; [Fe2+] = 11.9mM; initial pH = 3.2

1800
1600
1400
1200
Oxalic acid (mg/L)

1000
800
600
400
200
0
plate type rod type

Figure 4-19: Oxalic acid content of the treated high concentration aniline solution
using the plate type electrode and rod type electrode EF reactors. Experimental
condition: H2O2] = 640mM; [Fe2+] = 11.9mM; initial pH = 3.2

55
However after treatment of the aniline solution using the plate type electrode and
rod type electrode EF reactors, the solution BOD significantly increased to 240ppm and
323ppm for the plate type electrode and rod type electrode EF reactors respectively.
Likewise, the toxicity also decreased and had a value of 0.18 and 0.25 for the plate type
electrode and rod type electrode EF reactors respectively. The main biodegradable
component of the treated aniline solution was also determined in the study and the oxalic
acid concentration after treatment is shown in Figure 4-19. The oxalic acid content of the
treated solution was 1,607ppm for the plate type electrode EF reactor and 1,675ppm for
the rod type electrode EF reactor.

These results showed that further treatment of the aniline solution using existing
technologies like biological treatment systems is possible due to production of
biodegradable compounds like oxalic acid. However further treatment is also necessary in
order to achieve typical governmental standards for wastewater effluents. Therefore
preliminary treatment of high concentration aniline solution using the plate type electrode
or rod type electrode EF reactors would greatly enhance its biodegradability.

56
V. CONCLUSIONS

Based on the results obtained within the scope and limitations of the study, the
following conclusions can be made:

1. The EF process is more superior to the CF process due to its higher treatment
efficiency at low Fe2+ concentrations and low residual H2O2 after treatment. In addition to
this, previous studies concluded that the EF process produces low inorganic sludge than
the CF process.

2. The rod type electrode EF reactor has a higher Fe2+ regeneration ability than
the plate type electrode EF reactor.

3. At H2O2 concentrations greater than 87mM, both of the EF reactors have 100%
aniline removal efficiency. However, at H2O2 concentrations lower than 58mM, the plate
type electrode EF reactor is superior to the rod type electrode EF reactor because of the
inhibition of the excess electro regenerated Fe2+ with Fenton’s reaction. Aside from this,
application of electric current greater than 0.8A/L for both of the EF reactors also
resulted to a 100% aniline removal efficiency. However increasing the initial aniline
concentration at constant H2O2 and Fe2+ concentrations significantly decreases the
treatment efficiency of both of the EF reactors. In addition to this, the change in H2O2,
Fe2+ and initial aniline concentration affects the aniline removal efficiency significantly
than the change in electric current.

4. Increase of H2O2, Fe2+ and electric current increases the initial aniline
degradation rate. However further increase of the Fe2+ concentration greater than 1.07mM
had no further effect on the initial aniline degradation rate. An increase in the initial
aniline concentration significantly decreases the initial aniline degradation rate. Both of
the EF reactors have nearly the same initial aniline degradation rates at all experimental
conditions used. In addition to this, the change in Fe2+ and initial aniline concentration

57
affects the initial aniline degradation rate significantly than the change in H2O2 and
electric current.

5. The kinetic model for aniline degradation using the EF reactors followed the
second order behavior. The rate constants were determined to increase as the
concentrations of H2O2, Fe2+ and electric current were also increased. However further
increase of the applied electric current to 0.8A/L for the rod type electrode EF reactor and
1.8A/L for the plate type electrode EF reactor resulted into a significant decrease in the
rate constant. At H2O2 concentrations lower than 29mM, both of the EF reactors had the
same rate constants. However at high H2O2 concentrations, the rod type electrode EF
reactor have lower rate constants due to the higher competition of aniline degradation by
products with hydroxyl radical. At all Fe2+ concentrations used in the study the plate type
electrode EF reactor have higher rate constants. However at low applied electric currents,
it had lower rate constants due to insufficient amounts of electro regenerated Fe2+. In
addition to this, both of the EF reactors have the same rate constants at an initial aniline
concentration greater than 15mM. Fe2+ and initial aniline concentration had a greater
effect on the rate constant than the change in H2O2 and electric current.

6. An increase in the H2O2 and Fe2+ concentrations was determined to increase the
COD removal efficiency of both of the EF reactors. However further increase in Fe2+ and
electric current greater than 1.07mM and 0.4A/L had no further effect on the COD
removal efficiency. At low H2O2 concentrations, the rod type electrode EF reactor had
lower COD removal efficiencies due to inhibition of excess electro regenerated Fe2+.
Both of the EF reactors have nearly the same COD removal efficiencies at the Fe2+
concentrations and electric currents used in the study. However an increase in the initial
aniline concentration significantly decreases the COD removal efficiencies. The change
in Fe2+, H2O2 and initial aniline concentration significantly affects the COD removal
efficiency than electric current.

7. For both of the EF reactors, an increase in the concentrations of H2O2, Fe2+,


electric current and initial aniline concentrations significantly decreases the H2O2

58
efficiency for aniline and COD removal. Both of the EF reactors have the same H2O2
efficiencies at all concentrations of Fe2+, electric currents, and initial aniline
concentrations used in the study. However at very low H2O2 concentration, the rod type
electrode EF reactor had a higher H2O2 efficiency for aniline removal. However at H2O2
concentrations lower than 58mM, the rod type electrode EF reactor had lower H2O2
efficiencies for COD removal.

8. Aside from this, an increase in H2O2 and Fe2+ concentration lowered power
consumptions for aniline and COD removal for both of the EF reactors. However further
increase of H2O2 greater than 58mM and Fe2+ greater than 1.61 mM had no further effect
on power consumption due to decreased aniline and COD removal efficiencies. The rod
type electrode EF reactor consumes twice as much power for aniline and COD removal
than the plate type electrode EF reactor. In addition to this, COD removal requires twice
as much power than aniline removal due to its lower COD removal efficiencies. Increase
in applied electric current increases the power consumption for both of the EF reactors.
However the difference in the power consumption between the rod type electrode and
plate type electrode EF reactors also increases by 1.7 to 3.3 times. An increase in the
initial aniline concentration for plate type electrode EF reactor had no significant effect
on the power consumption for aniline and COD removal.

9. Both of the EF reactors have the same aniline and COD removal efficiencies
when a 10,000ppm COD of aniline solution was treated. Treatment of the high
concentration aniline solution resulted into an increased BOD and lowered toxicity of the
synthetic wastewater for both of the EF reactors. Therefore further treatment of the
wastewater through biological treatment systems is feasible.

59
VI. RECOMMENDATIONS FOR FUTURE WORK

The areas for future work identified during the conduct of this study are the
following:

1. Analyses of Total Organic Carbon (TOC) will investigate the aniline


degradation pathway by using the Average Oxidation States (AOS) index.

2. Scale up of the rod type electrode and plate type electrode EF reactors will
determine feasibility of full scale wastewater treatment applications.

3. Use of step wise addition of H2O2 and determine its effect on the H2O2
efficiency for aniline and COD removal using the rod type electrode and plate type
electrode EF reactors will determine optimum H2O2 usage for pollutant degradation.

4. Investigating the effect of anions and cations typically present in a real


wastewater stream using the laboratory scale rod type electrode and plate type electrode
EF reactors will establish the feasibility of real wastewater treatment applications.

5. Investigating the use of time delay in the electric current application for the
electro-Fenton reactors and its effects on the power consumption for aniline and COD
removal will determine optimum power usage and conservation.

6. A study on an electro-Fenton system coupled with a biological treatment


system will verify the feasibility of further degradation of byproducts through biological
treatment systems.

7. Research on the use of UV in an electro-Fenton system will determine its effect


on the treatment performance efficiency.

60
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APPENDIX D
Photographs of the electro-Fenton Reactors

D-1: Plate type electrode electro-Fenton Reactor.

The plexiglas rectangular vessel with the electrodes and mixers attached.

The electro-Fenton reactor attached to the power supply.

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D-2: Rod type electrode electro-Fenton reactor.

The cylindrical, stainless steel vessel with the electrodes, mixer and power supply.

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